KR20210099023A - Oily moisturizer and skin external composition comprising same - Google Patents

Abstract

The present invention is composed of an esterified product of component A and component B or an esterified product of component A, component B and component C, wherein the esterified product has a hydroxyl value of 0 to 160 mgKOH/g, and the component A and component B and a mass ratio of the fatty acid residue derived from component B and the fatty acid residue derived from component C in the fatty acid residue constituting the esterified product of component C is 99.9:0.1 to 45:55, and an oily moisturizer comprising the same A composition for external application to the skin is provided. Component A: dipentaerythritol, erythritol, or sorbitan, polyhydric alcohol Component B: One or more fatty acids selected from linear saturated fatty acids having 6 to 10 carbon atoms Component C: From fatty acids having 6 to 28 carbon atoms One or two or more fatty acids selected (however, component B is excluded)

Description

Oily moisturizer and skin external composition comprising same

The present invention relates to an esterified product composed of a specific polyhydric alcohol and a fatty acid, an oily moisturizer composed of the esterified product, and a composition for external use on the skin comprising the oily moisturizer.

So far, in the cosmetic field, as a moisturizing agent that prevents the skin from drying out and gives moisture to the skin, a water-soluble moisturizer such as polyethylene glycol, propylene glycol, glycerin, 1,3-butylene glycol, xylitol, sorbitol, and hyaluronic acid is used. It is frequently used (see Patent Document 1). In addition, many water-soluble moisturizers such as various natural extracts and extracts have been developed. However, after these water-soluble moisturizing agents are applied to the skin, they flow down from the skin due to sweating or washing off with water, and as a result, the moisture content of the skin may not be maintained.

On the other hand, although there are few examples as an oily moisturizer, oil agents, such as petrolatum, are known. The oil agent can suppress evaporation of water from the skin surface by clogging the skin. For this reason, in particular, petrolatum is widely used as a base for a composition for external use on the skin for the treatment, prevention or improvement of symptoms resulting from dry skin, specifically, mainly as a base for an ointment (see Patent Document 2). ).

Clearly, petrolatum, which is oily, has the advantage that it does not run off easily due to sweating or rinsing with water. However, due to the properties of Vaseline itself, when applied to the skin, it is sticky and has poor skin compatibility, so it may feel uncomfortable during use. In addition, when petrolatum applied to the skin is wiped off by contact with clothes or the like, the blocking effect cannot be exhibited, and as a result, the moisture content of the skin may not be maintained.

As an evaluation method of the moisturizing effect, so far, the evaluation based on the amount of transepidermal water evaporation (for example, refer to Patent Document 3) or the amount of moisture in each layer (for example, refer to Patent Documents 4 and 5.) The method is common. In fact, there are many patent documents evaluating the moisturizing effect by the amount of moisture in each layer.

In addition, in patent document 6, the moisturizing feeling of a cosmetic liquid is evaluated by the sensory evaluation of whether a moisturizing feeling is felt as a touch after apply|coating to the skin surface of a test subject. That is, evaluation of the moisturizing feeling is performed only by sensory evaluation, the moisture content of each layer is not investigated, and it is not clear whether the moisturizing function of the skin itself is improved by the application of the cosmetic liquid.

Japanese Laid-Open Patent Publication No. 11-209223 Japanese Patent No. 4385170 Japanese Patent No. 5954935 Japanese Patent No. 5572263 Japanese Patent No. 5917043 Japanese Patent No. 4377879

As a moisturizing agent blended in a composition for external use on the skin such as a cosmetic, development of a moisturizer having a more excellent moisturizing effect is expected.

It is an object of the present invention to provide an oily moisturizer excellent in moisturizing effect on the skin, and a composition for external use on the skin comprising the same. Specifically, it is to provide an oily moisturizing agent comprising an esterified product having a skin moisturizing function when applied to the skin, and a composition for external use on the skin comprising the same.

In view of the circumstances described above, the present inventors have repeatedly studied the moisturizing function of various oily substances, and as a result, the effect of the oily substances on the moisturizing function of the skin is applied to the skin surface, After waiting in that state for a predetermined time, the present invention was found to have a high moisturizing effect on the skin by investigation by a method of measuring the amount of moisture in each layer of the skin in a state in which the oily substance has been removed from the skin surface. came to completion. Specifically, the present invention provides the following.

[1] an esterified product of component A and component B or an esterified product of component A, component B and component C, wherein the esterified product has a hydroxyl value of 0 to 160 mgKOH/g;

The mass ratio of the fatty acid residue derived from the component B to the fatty acid residue derived from the component C in the fatty acid residue constituting the ester product of the component A, the component B and the component C is 99.9:0.1 to 45:55, characterized in that Oily moisturizer.

Component A: polyhydric alcohol, which is dipentaerythritol, erythritol, or sorbitan

Component B: one or two or more fatty acids selected from linear saturated fatty acids having 6 to 10 carbon atoms

Component C: one or more fatty acids selected from fatty acids having 6 to 28 carbon atoms (however, component B is excluded)

[2] The oily moisturizer according to the above [1], wherein the component A is dipentaerythritol.

[3] A composition for external use on the skin, comprising the oily moisturizer of [1] or [2].

[4] The composition for external use on the skin according to the above [3], wherein the composition for external use on the skin is a cosmetic, a face wash, a systemic cleansing agent, or an external pharmaceutical.

[5] A method for moisturizing the skin, wherein the composition for external use on the skin comprising the oily moisturizer of [1] or [2] is applied to the skin surface.

[6] an ester product of component A and component B having a hydroxyl value of 0 to 160 mgKOH/g, or

A component A, a component B, and a component having a hydroxyl value of 0 to 160 mgKOH/g and a mass ratio of the fatty acid residue derived from component B to the fatty acid residue derived from component C in the constituent fatty acid residues is 99.9:0.1 to 45:55; Use of C esterified products for moisturizing.

Component A: polyhydric alcohol, which is dipentaerythritol, erythritol, or sorbitan

Component B: one or two or more fatty acids selected from linear saturated fatty acids having 6 to 10 carbon atoms

Component C: one or more fatty acids selected from fatty acids having 6 to 28 carbon atoms (however, component B is excluded)

[7] an ester product of component A and component B having a hydroxyl value of 0 to 160 mgKOH/g, or

A component A, a component B, and a component having a hydroxyl value of 0 to 160 mgKOH/g and a mass ratio of the fatty acid residue derived from component B to the fatty acid residue derived from component C in the constituent fatty acid residues is 99.9:0.1 to 45:55; Use of an esterified product of C for producing a composition for external use on the skin.

Component A: polyhydric alcohol, which is dipentaerythritol, erythritol, or sorbitan

Component B: one or two or more fatty acids selected from linear saturated fatty acids having 6 to 10 carbon atoms

Component C: one or more fatty acids selected from fatty acids having 6 to 28 carbon atoms (however, component B is excluded)

ADVANTAGE OF THE INVENTION According to this invention, the oil-based moisturizer which consists of a specific esterified material and has a moisturizing effect when it applies to skin, and the skin external composition containing the said oil-based moisturizer can be obtained.

Hereinafter, embodiments of the present invention will be specifically described.

In this invention and this specification, an "oil-based moisturizer" means an agent having a moisturizing effect that does not dissolve in water at normal temperature and under normal pressure (eg, 20°C, 101.3 kPa). Here, when it melt|dissolves in water, when it mixes with water, it means that it becomes uniform, without forming a layer or becoming cloudy. In other words, when mixed with water, an oily humectant separates from water and forms a layer, or becomes cloudy by emulsification.

In the present invention and this specification, the moisturizing effect means an effect of improving the moisturizing function of the skin, and more specifically, an effect of maintaining or increasing the moisture content of each layer. The oily moisturizer according to the present invention maintains or increases the moisture content of each layer for a certain period of time not only in the state of being applied to the skin, but also when a part or most of the composition for external use is removed from the surface of the skin after application to the skin. It is desirable that the effect be maintained.

The moisture content of each layer can be investigated by the electrical conductivity (μS) of each layer. The electrical conductivity (μS) of each layer depends on the moisture content of each layer, and as the moisture content of each layer increases, the electrical conductivity (μS) of each layer increases. The electrical conductivity (µS) of each layer can be measured by a static pressure sensor probe contact high frequency conductance exchange method. Specifically, the electrical conductivity (μS) of each layer can be measured by using a moisture content measuring device for each layer based on the measurement method, for example, “SKICON-200” for measuring moisture content for each layer manufactured by IBS.

The hydroxyl value (mgKOH/g) of the esterified product is 2.3.6.2-1996 Hydroxyl value (pyridine-acetic anhydride) of the "Japan Oil Chemical Society Establishment Standard Oil and Oil Analysis Test Method 2013 Edition" published by the Japan Oil Chemical Society. Act) can be measured by

Specifically, it is the mg number of potassium hydroxide required to neutralize the acetic acid bonded to the hydroxyl group when 1 g of the sample is acetylated. The hydroxyl value of the esterified product is measured by a neutralization titration method. More specifically, after adding an acetylation reagent to the sample and heating in a glycerin bath for 1 hour, unreacted acetic anhydride is replaced with acetic acid in 1 ml of water, a phenolphthalein solution is added as an indicator, and titration is performed with a potassium hydroxide ethanol solution. do. A hydroxyl value is computed from the quantity of the potassium hydroxide ethanol solution required for the color development of phenolphthalein to be confirmed. An acetylation reagent is a solution which added pyridine to 25 g of acetic anhydride, and prepared the whole quantity to 100 ml.

<oily moisturizer>

The oily moisturizer according to the present invention is composed of an esterified product of component A and component B or an esterified product of component A, component B and component C, and the esterified product has a hydroxyl value of 0 to 160 mgKOH/g. In the esterified product, the esterified product of component A, component B, and component C has a mass ratio of a fatty acid residue derived from component B and a fatty acid residue derived from component C in the fatty acid residue constituting the esterified product, 99.9:0.1 to It is 45:55.

Component A: polyhydric alcohol, which is dipentaerythritol, erythritol, or sorbitan

Component B: one or two or more fatty acids selected from linear saturated fatty acids having 6 to 10 carbon atoms

Component C: one or more fatty acids selected from fatty acids having 6 to 28 carbon atoms (however, component B is excluded)

The polyhydric alcohol of component A is dipentaerythritol, erythritol, or sorbitan. Dipentaerythritol uses pentaerythritol as a raw material, can be obtained by a condensation reaction, etc., and is marketed. Moreover, sorbitan uses sorbitol as a raw material, can be obtained by an intramolecular condensation reaction, etc., and is marketed.

As a commercial item of dipentaerythritol, Dipentaerythritol (90% GRADE) sold by Jang-Young Lee Chemical Co., Ltd. As a commercial item of erythritol, erythritol sold by Bussan Food Science, as a commercial item of sorbitan, sorbitan sold by Sanko Chemical Industries, Ltd. M-70 etc. are mentioned.

As a polyhydric alcohol of component A, since a higher moisturizing effect is acquired, dipentaerythritol is preferable.

The fatty acid of component B is a C6-C10 linear saturated fatty acid. Specific examples of the linear saturated fatty acid having 6 to 10 carbon atoms include caproic acid (n-hexanoic acid: 6 carbon atoms), n-heptanoic acid (7 carbon atoms), caprylic acid (n-octanoic acid: 8 carbon atoms); and pelargonic acid (n-nonanoic acid: 9 carbon atoms) and capric acid (n-decanoic acid: 10 carbon atoms), preferably one or two selected from caprylic acid and capric acid, Prylic acid is more preferable.

The fatty acid of component C is a C8-C22 fatty acid, and it is preferable that it is a C8-18 fatty acid. Moreover, a linear saturated fatty acid may be sufficient as the said fatty acid, a branched saturated fatty acid may be sufficient, a linear unsaturated fatty acid may be sufficient, and a branched unsaturated fatty acid may be sufficient as it. Moreover, a hydroxyl-containing fatty acid may be sufficient. Among these, linear saturated fatty acids or branched saturated fatty acids are preferable, and linear saturated fatty acids are more preferable. Moreover, in addition to monovalent fatty acid, polyhydric fatty acid can also be used. As a fatty acid of component C, these 1 type, or 2 or more types can be used. However, a C6-C10 linear saturated fatty acid (component B) is excluded.

Specific examples of linear saturated fatty acids having 11 to 28 carbon atoms include n-undecanoic acid (11 carbon atoms), lauric acid (n-dodecanoic acid: 12 carbon atoms), myristic acid (14 carbon atoms), palmitic acid ( 16), stearic acid (18 carbon atoms), behenic acid (22 carbon atoms), and montanic acid (28 carbon atoms).

Examples of the linear unsaturated fatty acid having 6 to 28 carbon atoms include palmitoleic acid (16 carbon atoms), oleic acid (18 carbon atoms), linoleic acid (18 carbon atoms), linolenic acid (18 carbon atoms), and erucic acid (22 carbon atoms). there is.

Specific examples of branched saturated fatty acids having 6 to 28 carbon atoms include 2-ethylhexanoic acid (8 carbon atoms, also called isocaprylic acid), 3,5,5-trimethylhexanoic acid (9 carbon atoms, also called isononanoic acid). ), 2-butyloctanoic acid (10 carbon atoms), isoundecanoic acid (11 carbon atoms), 2-butyloctanoic acid (12 carbon atoms, also called isolauric acid or isododecanoic acid), isotridecanoic acid (13 carbon atoms), isopalmitic acid (16 carbon atoms), isostearic acid (3 types having 18 carbon atoms and different branching states), and octyldodecanoic acid (20 carbon atoms), and the like.

Examples of the hydroxyl group-containing fatty acid having 6 to 28 carbon atoms include 12-hydroxystearic acid (18 carbon atoms) and ricinolic acid (18 carbon atoms).

A dibasic acid is mentioned as a C6-C28 polyhydric fatty acid. Specifically, suberic acid (octanedioic acid: 8 carbon atoms), azelaic acid (nonanedioic acid: 9 carbon atoms), sebacic acid (decanedioic acid: 10 carbon atoms), undecanedioic acid (11 carbon atoms), dodecanedioic acid (12 carbon atoms) ), tridecanedioic acid (number of carbons: 13), tetradecanedioic acid (number of carbons: 14), pentadecanedioic acid (number of carbons: 15), hexadecanedioic acid (number of carbons: 16), heptadecandioic acid (number of carbons: 17), octadecanedioic acid (carbon number: 18), nonadecandioic acid (carbon number: 19), eicosic acid diacid (carbon number: 20), isoeic acid diacid (carbon number: 20), and octacoic acid diacid (carbon number: 28).

As the saturated fatty acid of the component B and the fatty acid of the component C, a chemically synthesized synthetic product may be used, or a product extracted from a natural product may be used. Moreover, as for the component B and the component C, a commercial item can also be used for both.

When the esterified product which is the oily moisturizing agent according to the present invention is an esterified product of component A, component B, and component C, the amount of fatty acid residue derived from component C in the fatty acid residue constituting the esterified product is the amount of the fatty acid residue in the polyhydric alcohol of component A. What is necessary is just an amount which does not impair the moisturizing effect of the skin obtained by introduce|transducing the fatty acid residue derived from the component B to a hydroxyl group by an esterification reaction. The mass ratio of the fatty acid residues derived from component B to the fatty acid residues derived from component C in the fatty acid residues constituting the esterified product (hereinafter referred to as “mass ratio of fatty acid residues constituting component B and component C” in some cases) is , 99.9:0.1 to 45:55, preferably 99.9:0.1 to 50:50, and more preferably 99.9:0.1 to 80:20.

The mass ratio of the constituent fatty acid residues of the component B and the component C in the constituent fatty acids of the esterified product can be measured, for example, as follows. The fatty acid residue in the esterified product as a publicly disclosed sample was subjected to the 2.4.1.1-2013 methyl esterification method (sulfuric acid-methanol method) (published by the Japan Oil Chemical Society, “Japan Oil Chemical Society Establishment Standard Oils and Oils Analysis Test Method 2013 Edition”) or A methyl esterified derivative is prepared by a method corresponding thereto. Methyl esterification methods, such as the 2.4.1.2-2013 boron trifluoride-methanol method and 2.4.1.3-2013 sodium methoxide method of the same standard oil-fat analysis test method, can also be referred to preparation of this methyl-esterified derivative.

The obtained derivative was analyzed by 2.4.2.3-2013 fatty acid composition (capillary gas chromatograph method) (published by the Japan Oil Chemical Society, "Japan Oil Chemical Society Establishment Standard Oils and Oils Analysis Test Method 2013 Edition") or an equivalent method The mass ratio of the constituent fatty acid residues of the component B and the component C in the constituent fatty acids of the esterified product can be determined by the method of isolating and measuring by .

For example, when saturated and unsaturated fatty acids having 18 carbon atoms are mixed, instead of the total mass ratio of saturated and unsaturated fatty acids having 18 carbon atoms, if you want to know each component separately, 2.4.2.3-2013 fatty acid composition (capillar gas chromatography), stearic acid, oleic acid, linoleic acid, linolenic acid, and the like can be separated.

More specifically, a derivative obtained by methyl esterification of a fatty acid residue in the esterified product is prepared by dissolving an esterified product as a test sample in a derivatization reagent and heating it. The obtained derivative is separated for each type of fatty acid methyl ester by a gas chromatograph equipped with FID, and quantified. The composition of the fatty acid residue of the esterified product can be determined based on the percentage (%) of the peak area of the fatty acid methyl ester obtained from each fatty acid residue with respect to the total of the peak areas on the chromatograph. By preparing a derivative obtained by methyl esterification with respect to a fatty acid raw material for which the mass ratio of the fatty acid residues constituting component B and component C is known in advance, and analyzing this with a gas chromatograph, the composition of component B and component C in the esterified product is more accurately The mass ratio of fatty acid residues can be confirmed.

In the oily moisturizer according to the present invention, at least a part of the hydroxyl groups in the polyhydric alcohol of the component A is substituted with a fatty acid residue derived from the fatty acid of the component B by an esterification reaction, and the hydroxyl value is 0 to 160 mgKOH/g The esterified product or the fatty acid residue derived from the fatty acid of component B and the fatty acid residue derived from the fatty acid of component C are substituted, and the mass ratio of the fatty acid residue derived from component B to the fatty acid residue derived from component C is 99.9: It is 0.1-45:55 and consists of an esterified product with a hydroxyl value of 0-160 mgKOH/g. By setting the hydroxyl value of the esterified product within a specific range, the esterified product can have a moisturizing effect on the skin.

The oil-based moisturizing agent according to the present invention can have a moisturizing effect as long as the hydroxyl value of the esterified product constituting it is 0 to 160 mgKOH/g. By changing the value of the hydroxyl value of the esterified product constituting the oil-based moisturizing agent according to the present invention, the viscosity and feel of the esterified product can be adjusted to a desired state. For this reason, as an oil-based moisturizer according to the present invention, esterified products having different hydroxyl values can be appropriately used according to the use or prescription circumstances.

The viscosity and texture of the esterified product as the oily moisturizing agent according to the present invention is also affected by the type and composition of the fatty acid residue in the esterified product. For this reason, by adjusting the kind of fatty acid of component B and fatty acid of component C, and the esterification efficiency of component A with a polyhydric alcohol, the esterified material provided with a desired viscosity and a texture can be obtained. For example, by limiting the fatty acid of component B to at least one of caprylic acid and capric acid in particular, the viscosity of an esterified product can be made lower. And when the esterified material with low viscosity is apply|coated to skin, there is little stickiness, and it becomes a refreshing touch. For this reason, the composition for external use for skin containing the esterified product of the component B with a fatty acid as an oily moisturizer has good skin compatibility and excellent usability.

When the fatty acid residue derived from the fatty acid of component C is contained in the fatty acid residue in the esterified product, the feel and various physical properties when the esterified product is applied to the skin surface can be improved. That is, by appropriately adjusting the type and abundance ratio (esterification rate) of fatty acid residues derived from the fatty acid of component C in the esterified product, it has a moisturizing effect and has a desired texture and physical properties, so that an esterified product very useful as an oily moisturizer is obtained. can

The esterified product which is an oily moisturizer according to the present invention uses component A and component B or component A and component B and component C as reaction raw materials, and esterifies these reaction raw materials so that the hydroxyl value is within a specific range. It is the esterified product obtained by carrying out.

The esterified product in which component A is dipentaerythritol may contain fatty acid esters having a degree of esterification of 1 to 6. The composition ratio of the dipentaerythritol fatty acid ester having an esterification degree of 1 to 6 is not particularly limited as long as the hydroxyl value of the esterified product is 0 to 160 mgKOH/g. In addition, this composition ratio can be adjusted by suitably adjusting the preparation ratio of a raw material, and reaction conditions of an esterification reaction.

The esterified product in which component A is erythritol may contain fatty acid esters having a degree of esterification of 1 to 4. The composition ratio of the erythritol fatty acid ester having an esterification degree of 1 to 4 is not particularly limited as long as the hydroxyl value of the esterified product is 0 to 160 mgKOH/g. In addition, this composition ratio can be adjusted by suitably adjusting the preparation ratio of a raw material, and reaction conditions of an esterification reaction.

The esterified product in which component A is sorbitan may contain fatty acid esters having a degree of esterification of 1 to 4. The composition ratio of the sorbitan fatty acid ester having an esterification degree of 1 to 4 is not particularly limited as long as the hydroxyl value of the esterified product is 0 to 160 mgKOH/g. In addition, this composition ratio can be adjusted by suitably adjusting the preparation ratio of a raw material, and reaction conditions of an esterification reaction.

Among the esterified products of the oily moisturizing agent according to the present invention, the esterification reaction for obtaining the esterified product of the component A and the component B is, for example, the component B required to obtain the desired hydroxyl value with respect to 1 mole of the component A It can carry out by injecting the number of moles or a number of moles larger than that, and reacting at a temperature of 180 to 240°C in the absence of a catalyst or in the presence of a catalyst. As the catalyst, it is possible to apply a catalyst used in the esterification of an alcohol and a fatty acid, for example, an acid, an alkali or a catalyst known per se in the field of organic chemistry. The said reaction may be performed in the solvent which does not have a bad influence on the esterification reaction, and may be performed without a solvent. As the solvent, a solvent known per se in the field of organic chemistry, which is used for the esterification reaction of an alcohol and a fatty acid, can be applied. As reaction time, 10 hours - 20 hours are usually applicable. Moreover, the reaction time may be 10 hours or less or 20 hours or more because it is influenced by the raw material (linear or branched) used, the presence or absence of a catalyst, the esterification temperature, or an excess amount of an acid. After completion of the reaction, when the catalyst is used, the catalyst may be removed by filtration treatment, adsorption treatment, or the like. From the reaction product of the esterification reaction, an esterified product can be obtained by a conventional method such as removing and purifying excess unreacted raw material by distillation or purifying under alkaline conditions. In addition, when it is desired to improve the color of the esterified product, the color may be improved by decolorization treatment by a conventional method.

Here, by adjusting the injection amounts of component A and component B, and calculating so that it may become the target hydroxyl value, the esterified product of the vicinity of the target hydroxyl group can be obtained.

For example, when component A is dipentaerythritol and an ester product having a hydroxyl value of 0 mgKOH/g is prepared, that is, a full ester of fatty acid of dipentaerythritol (fatty acid at all hydroxyl groups of dipentaerythritol) In the case of producing this esterified product), it can be produced by injecting the component B in an amount greater than 6 moles with respect to 1 mole of the component A.

In addition, when component A is erythritol or sorbitan and an ester product having a hydroxyl value of 0 mgKOH/g is produced, that is, erythritol or a full ester of sorbitan fatty acid (erythritol or sorbitan When all fatty acids are esterified), it can be prepared by injecting component B in an amount greater than 4 moles with respect to 1 mole of component A.

In addition, when component A is dipentaerythritol and an ester product having a hydroxyl value of greater than 0 mgKOH/g is produced, that is, a partial ester of a fatty acid of dipentaerythritol (a fatty acid at a partial hydroxyl group of dipentaerythritol) When producing this esterified thing), it can manufacture by injecting less than 6 mol of component B with respect to 1 mol of component A, and completing reaction.

In addition, when component A is erythritol or sorbitan and an ester product having a hydroxyl value greater than 0 mgKOH/g is prepared, that is, erythritol or a partial ester of sorbitan fatty acid (erythritol or sorbitan) In the case of producing a fatty acid esterified with a partial hydroxyl group of the component A), it can be prepared by adding the component B in an amount less than 4 moles to 1 mole of the component A and completing the reaction.

Moreover, even if the component A is dipentaerythritol, erythritol, or sorbitan in any case, in the production of a partial ester having a target hydroxyl value, a larger amount than the required component B is injected, and the acid value during the reaction Also by a method of stopping the reaction halfway while observing the change of

In addition, in any case of component A, dipentaerythritol, erythritol, and sorbitan, when the hydroxyl value of the obtained esterified product deviates from the target hydroxyl value, the injection ratio is set in consideration of the degree of deviation, Finally, an esterified product having a desired hydroxyl value can be obtained.

In the production of an esterified product of component A, component B, and component C, which are oily moisturizing agents according to the present invention, the esterification reaction for obtaining an esterified product having a desired hydroxyl value is, for example, to 1 mole of component A, In order to set it as the target hydroxyl value, the number of moles of component B and component C required, or the number of moles larger than it are injected|poored, and it can carry out by making it react at 180-240 degreeC in the presence of a catalyst or a non-catalyst. Purification after completion of the reaction may be carried out in the same manner as described above.

Here, by adjusting the injection amounts of the component A, the component B, and the component C, and calculating so that the target hydroxyl value is obtained, an esterified product having a target hydroxyl group in the vicinity can be obtained.

For example, when component A is dipentaerythritol and an ester product having a hydroxyl value of 0 mgKOH/g is prepared, that is, a full ester of fatty acid of dipentaerythritol (fatty acid at all hydroxyl groups of dipentaerythritol) When preparing this esterified product), it can be prepared by injecting components B and C in an amount greater than 6 moles with respect to 1 mole of component A.

In addition, when component A is erythritol or sorbitan and an ester product having a hydroxyl value of 0 mgKOH/g is produced, that is, erythritol or a full ester of sorbitan fatty acid (erythritol or sorbitan When all fatty acids are esterified), it can be prepared by injecting components B and C in an amount greater than 4 moles with respect to 1 mole of component A.

In addition, when component A is dipentaerythritol and an ester product having a hydroxyl value of greater than 0 mgKOH/g is produced, that is, a partial ester of a fatty acid of dipentaerythritol (a fatty acid at a partial hydroxyl group of dipentaerythritol) In the case of producing this esterified product), it can be prepared by adding components B and C in an amount of less than 6 moles to 1 mole of component A and completing the reaction.

In addition, when component A is erythritol or sorbitan and an ester product having a hydroxyl value greater than 0 mgKOH/g is prepared, that is, erythritol or a partial ester of sorbitan fatty acid (erythritol or sorbitan) In the case of producing a fatty acid esterified with a hydroxyl group of a part of the component A, it can be prepared by injecting less than 4 moles of the component B and the component C with respect to 1 mole of the component A and completing the reaction.

In addition, even if the component A is any of dipentaerythritol, erythritol, and sorbitan, in the production of a partial ester having a target hydroxyl value, a larger amount than the required component B and component C is injected, Also by a method of stopping the reaction halfway while observing the change in acid value during the reaction, an esterified product having a target hydroxyl group in the vicinity can be obtained.

In addition, in the case where component A is dipentaerythritol, erythritol, or sorbitan in any case, when the hydroxyl value of the obtained esterified product deviates from the target hydroxyl value, the injection ratio is made in consideration of the degree of deviation, Finally, an esterified product having a desired hydroxyl value can be obtained.

In addition, when the total amount of component B and component C is injected in an amount larger than the number of moles of component B and component C required to make the target hydroxyl value, the reactivity of component C is lower than the reactivity of component B, component B reaction proceeds first, and the mass ratio of the constituent fatty acid residues of the component B and the component C in the resulting esterified product may deviate from the mass ratio of the injected constituent fatty acid residues. In such a case, by adjusting the mass ratio of the injection amount of each component in consideration of the deviation in advance, or by carrying out a two-stage reaction of first injecting and reacting the fatty acid of the component C with low reactivity, and then injecting the component B to react , the mass ratio of constituent fatty acid residues of component B and component C can be adjusted.

One aspect of the esterified product which is an oily moisturizer according to the present invention is an esterified product of component A and component B, wherein component A is dipentaerythritol, erythritol, or sorbitan, and component B is a direct compound having 6 to 10 carbon atoms. It is a fatty acid of 1 type or 2 types or more selected from chain saturated fatty acid, and a hydroxyl value is 0-160 mgKOH/g. Preferably, an ester of dipentaerythritol (component A) having a hydroxyl value of 0 to 160 mgKOH/g and one or more fatty acids (component B) selected from linear saturated fatty acids having 6 to 10 carbon atoms. dipentaerythritol (component A), more preferably a hydroxyl value of 0 to 160 mgKOH/g, and one or two or more fatty acids selected from caprylic acid and capric acid (component B) is an ester of

One aspect of the esterified product which is an oily moisturizer according to the present invention is an esterified product of component A, component B, and component C, wherein component A is dipentaerythritol, erythritol, or sorbitan, and component B has 6 to C6 It is one or two or more fatty acids selected from the linear saturated fatty acids of 10, and component C is one or two or more fatty acids selected from fatty acids having 6 to 28 carbon atoms (however, component B is excluded), and an esterified product The mass ratio of the component B and the fatty acid residue constituting the component C in the fatty acid residue constituting the is 99.9:0.1 to 45:55, and the hydroxyl value is 0 to 160 mgKOH/g. Preferably, one or two selected from dipentaerythritol (component A) and a linear saturated fatty acid having 8 to 10 carbon atoms (component B) and one or two selected from fatty acids having 8 to 18 carbon atoms It is an esterified product of more than one type of fatty acid (component C), a hydroxyl value of 0 to 160 mgKOH/g, and a mass ratio of the constituent fatty acid residues of component B to component C of 99.9:0.1 to 45:55, more preferably is one or more fatty acids (component B) selected from dipentaerythritol (component A), caprylic acid and capric acid, and one or more fatty acids selected from fatty acids having 8 to 18 carbon atoms ( As an esterified product of component C), it is an esterified product having a hydroxyl value of 0 to 160 mgKOH/g and a mass ratio of the constituent fatty acid residues of component B and component C of 99.9:0.1 to 45:55.

In the oil-based moisturizer according to the present invention, the moisturizing effect is the effect that the electrical conductivity (μS) of each layer of the skin after application of the oil-based moisturizer is at least 50 μS or higher than the electrical conductivity (μS) of each layer before application It is preferable that it is an effect which can be set as at least 60 microS or more, It is more preferable that it is an effect which can be made into at least 70 microS or more.

When examining the moisturizing effect of an oil-based moisturizer, the electrical conductivity (μS) of each layer is measured in an environment in which room temperature and humidity are within a certain range, for example, 18 to 22°C, and an environment controlled to 40 to 55%RH. do. More specifically, for example, an oil-based moisturizer is uniformly applied to the skin surface in which the electrical conductivity (µS) of each layer has been previously measured. After the oil-based moisturizer is applied and maintained for a certain period of time, for example, 30 to 90 minutes, the oil-based moisturizer is removed from the skin surface. After removal for a certain period of time, for example, after 5 to 60 minutes have elapsed, the electrical conductivity (µS) of each layer to which the oil-based moisturizing agent has been applied is measured. A moisturizing effect value is calculated using the value of the electrical conductivity (μS) of each layer before and after application of the obtained oil-based moisturizing agent, and the moisturizing effect is evaluated.

In addition, it is preferable to perform evaluation of the moisturizing effect of an oil-based moisturizer at a time when skin tends to dry.

By mixing the esterified product which is the oil-based moisturizer according to the present invention with other ingredients, it can be prepared as a composition for external use on the skin applied to the body surface of an animal for moisturizing. Even an ester product solidified at room temperature can be used as liquid oil by dissolving it in liquid oil.

The other component is not particularly limited as long as it does not excessively impair the moisturizing effect of the esterified product, and may be appropriately selected from various additives permitted to be contained in cosmetics, cleaning agents, external pharmaceuticals, and the like. As said other component, for example, an oil-based component (except the oil-based moisturizer according to the present invention), an aqueous component, a polymer emulsion, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, a lipophilic nonionic Surfactants, hydrophilic nonionic surfactants, natural surfactants, humectants (excluding oil-based humectants related to the present invention), thickeners, preservatives, powder ingredients, pigments, pH adjusters, antioxidants, UV absorbers, fragrances, pigments, metals An ion sequestrant agent, purified water, etc. are mentioned. Specific examples include the same components as those that can be included in the composition for external use for skin described later.

The oily moisturizer according to the present invention can be used as a raw material for various external composition for skin. By blending the oily moisturizing agent with various external composition for skin, the skin moisturizing effect can be imparted to the composition for external use for skin.

<Composition for external use on the skin>

Next, the composition for external use on the skin according to the present invention will be described.

The composition for external use on skin according to the present invention contains the oil-based moisturizer according to the present invention, and the oil-based moisturizer itself can also be used as an external composition for skin.

Here, in the present invention and the present specification, "composition for external use on the skin" means all external compositions externally applied to the body surface such as skin, nails, and hair, such as cosmetics, cleaning agents, quasi-drugs, and external pharmaceuticals. The composition for external use on skin according to the present invention is preferably a composition for external use on the skin in which at least one purpose of use is to moisturize the body surface tissues of animals such as humans, such as the skin, and is used for moisturizing the skin Cosmetics for moisturizing, cleansing agents for moisturizing, quasi-drugs for moisturizing, or external pharmaceuticals for moisturizing are more preferable.

Since the composition for external application for skin according to the present invention contains the oily moisturizer according to the present invention, by attaching it to the skin, the moisturizing function of the skin can be improved and the skin can be moisturized. In particular, the oil-based moisturizer according to the present invention can maintain a high moisture content in each layer of the skin even after being wiped off after being applied to the skin, and can maintain a moisturizing state. For this reason, the composition for external use for skin according to the present invention containing this oily moisturizer is not only applied to the skin, but also part or most of the composition for external use on the skin from the skin surface by sebum, sweat, rubbing and washing after application to the skin. Even when this has been removed, the moisturizing effect can be maintained for a certain period of time.

The composition for external use on the skin according to the present invention is used by being attached to the body surface of an animal. The body surface to which the composition for external use for skin is applied is not particularly limited, and examples thereof include skin, nails, and hair. The mode of adhesion of the composition for external use to the body surface is not particularly limited, and the composition for external use for skin may be applied to the body surface or sprayed.

The subject using the composition for external application for skin according to the present invention, that is, the subject requiring skin moisturization is not particularly limited, but it is preferably an animal. The animal may be a human or an animal other than a human. Since the oily moisturizer according to the present invention has a high moisturizing effect, the external composition for skin according to the present invention can be used for animals that require moisturizing of skin and hair, for example, animals living in a dry environment; It is preferably used for animals in need of treatment, prevention or amelioration of symptoms resulting from dry skin. Examples of symptoms resulting from dry skin include dry skin such as redness, eczema, and cracks, dry dermatitis, atopic dermatitis, and senile skin pruritus. For example, by applying to the skin surface an external pharmaceutical such as a cosmetic containing the oil-based moisturizer according to the present invention or an ointment containing the oil-based moisturizer according to the present invention as a substrate to the skin surface, the oil-based moisturizer according to the present invention is not included It can be expected that the decrease in the moisture content of each layer of the skin is suppressed, and the symptoms resulting from the drying of the skin are improved compared to the case where cosmetics or external pharmaceuticals are applied.

There is no restriction|limiting in particular about the use, formulation, etc. of the composition for skin external use which concerns on this invention, It may be a cosmetic, a cleaning agent, a quasi-drug, or an external drug may be sufficient. In addition, the composition for external use on skin according to the present invention is transparent (state: for example, solubilized or dissolved), translucent (state: for example, dispersed in a particulate state), cloudy (state: for example, dispersed) state or emulsified state), and two-layer separation (state: state separated into two layers), etc. may be any external appearance. For example, the composition for external use on the skin according to the present invention can be made into a variety of compositions for external use on the skin in which an oily component has been used conventionally. Specific examples of the cosmetic include skin care cosmetics such as emulsion, cosmetic liquid, cream, lotion, cosmetic oil, emollient cream, and hand cream; Hair cosmetics such as conditioner, hair conditioner, hair wax, and hair cream; make-up cosmetics such as solvent-based unseasoning; and sunscreen cosmetics such as sun oil and emulsified sunscreen. Specific examples of the cleaning agent include cleaning agents for hair such as cleansing oil, cleansing cream, face wash, body wash, and shampoo. Specific examples of external pharmaceuticals include coating agents such as creams, ointments, and lotions, and patches such as patches and plasters. There is no restriction|limiting in particular in the manufacturing method of these external skin composition, It can manufacture by a well-known method.

The composition for external use on skin according to the present invention can be produced by using the oily moisturizing agent according to the present invention as a raw material. The oil-based moisturizer according to the present invention can be easily formulated in the same way as many oil-based raw materials. Since the oily moisturizer according to the present invention is oily, when it is used as a raw material for an external composition for skin, the composition for external use for skin according to the present invention can be efficiently produced by mixing it with an oily component among other raw materials. The oil-based moisturizing agent according to the present invention is not mixed with the oil-based component among other raw materials, but is dispersed in an aqueous medium by emulsification, or a composition for external use on the skin can be prepared by solubilizing it in an aqueous medium.

The content of the oil-based moisturizer according to the present invention in the composition for external use for skin according to the present invention is not particularly limited, as long as it is an amount capable of exhibiting the skin moisturizing effect of the oil-based moisturizer.

The content of the oily humectant according to the present invention is determined by the type of other components, the composition for external application to the skin, the usage mode (whether applied to the skin and not intentionally removed from the skin surface, or from the skin surface within a certain period of time after application). It can be appropriately determined in consideration of whether it is an aspect to be removed.) and the like. For example, the content of the oily moisturizing agent according to the present invention in the composition for external use for skin according to the present invention can be appropriately determined within the range of 0.001 to 99.9 mass% with respect to the total mass of the composition for external use for skin.

In the composition for external application for skin according to the present invention, if necessary, various components generally used for external composition for skin can be blended within a range that does not impair the effects of the present invention. As such components, although it varies depending on the use and formulation of the composition for external use on the skin, for example, an oily component (excluding the oily moisturizer according to the present invention), an aqueous component, a polymer emulsion, an anionic surfactant, a cationic interface Active agents, amphoteric surfactants, lipophilic nonionic surfactants, hydrophilic nonionic surfactants, natural surfactants, humectants (excluding oily humectants related to the present invention), thickeners, preservatives, powder ingredients, pigments, pH adjusters, An antioxidant, a ultraviolet absorber, a fragrance|flavor, a pigment|dye, a sequestering agent, purified water, etc. are mentioned.

Examples of the oily component include liquid paraffin, heavy liquid isoparaffin, solid paraffin, α-olefin oligomer, squalane, petrolatum, polyisobutylene, polybutene, montan wax, ceresin wax, microcrystalline wax, polyethylene hydrocarbons such as wax and Fischer-Tropsch wax; oils and fats such as olive oil, castor oil, jojoba oil, mink oil, and macadamia nut oil; waxes such as beeswax, candelilla wax, spermaceti, carnauba wax, and wax wax; Cetyl 2-ethylhexanoate, isopropyl myristate, isopropyl palmitate, octyldodecyl myristate, polyglyceryl diisostearate, polyglyceryl triisostearate, diglyceryl triisostearate, tetra Polyglyceryl isostearate, diglyceryl tetraisostearate, trioctanoin, diisostearyl malate, neopentyl glycol dioctanoate, propylene glycol didecanoate, cholesterol fatty acid ester, glyceryl tristearate, glycerin fatty acid ester Eico esters such as acid diacid condensates, dextrin palmitic acid, dextrin myristic acid, and dextrin fatty acid ester; fatty acids such as stearic acid, lauric acid, myristic acid, behenic acid, isostearic acid, and oleic acid; higher alcohols such as stearyl alcohol, cetyl alcohol, lauryl alcohol, oleyl alcohol, isostearyl alcohol, behenyl alcohol, octyldodecanol, and isohexadecyl alcohol; Low polymerization degree dimethylpolysiloxane, high polymerization degree dimethylpolysiloxane, methylphenylpolysiloxane, decamethylcyclopentasiloxane, octamethylcyclotetrasiloxane, polyether-modified polysiloxane, polyoxyalkylene/alkylmethylpolysiloxane/methylpolysiloxane copolymer, and alkoxy-modified polysiloxane silicones; fluorine-based emulsions such as perfluorodecane, perfluorooctane, and perfluoropolyether; amino acid ester emulsions such as N-acylglutamic acid such as stearoylglutamic acid and N-lauroyl-L-glutamic acid di(cholesteryl or phytosteryl behenyl/octyldodecyl); and lanolin derivatives such as lanolin, liquid lanolin, lanolin acetate, liquid lanolin acetate, isopropyl lanolin fatty acid, and lanolin alcohol. These oily components may be used independently and may be used in combination of 2 or more type.

As said aqueous component, For example, glycols, such as lower alcohols, such as ethyl alcohol and butyl alcohol, propylene glycol, 1, 3- butylene glycol, dipropylene glycol, and polyethyleneglycol; Glycerols, such as glycerol, diglycerol, and polyglycerol; and plant extracts such as aloe vera, witch hazel, hamamelis, cucumber, tomato, apple, lemon, lavender, and rose. These aqueous components may be used independently and may be used in combination of 2 or more type.

Examples of the polymer emulsion include an alkyl acrylate polymer emulsion, an alkyl methacrylate polymer emulsion, an alkyl acrylate copolymer emulsion, an alkyl methacrylate copolymer emulsion, an acrylic acid/alkyl acrylate copolymer emulsion, and methacrylic acid/methacrylic acid. Alkyl acid copolymer emulsion, alkyl acrylate styrene copolymer emulsion, alkyl methacrylate styrene copolymer emulsion, vinyl acetate polymer emulsion, polyvinyl acetate emulsion, vinyl acetate containing copolymer emulsion, vinyl pyrrolidone styrene copolymer emulsion , and silicone-containing copolymer emulsions. These polymer emulsions may be used independently and may be used in combination of 2 or more type.

Examples of the anionic surfactant include fatty acid soaps such as soap base, sodium laurate and sodium palmitate, higher alkyl sulfate ester salts such as sodium lauryl sulfate and potassium lauryl sulfate; alkyl ether sulfate ester salts such as polyoxyethylene (POE)-lauryl sulfate triethanolamine and POE-lauryl sulfate sodium; N-acyl sarcosine acids, such as sodium lauroyl sarcosine; higher fatty acid amide sulfonates such as sodium N-myristoyl-N-methyl taurate, sodium methyl taurate of palm oil fatty acid, and sodium lauryl methyl taurate; phosphoric acid ester salts such as sodium POE-oleyl ether phosphate and POE-stearyl ether phosphoric acid; sulfosuccinates such as sodium di-2-ethylhexyl sulfosuccinate, sodium monolauroyl monoethanolamide polyoxyethylene sulfosuccinate, and sodium lauryl polypropylene glycol sulfosuccinate; Alkylbenzenesulfonates, such as linear dodecyl benzene sulfonate sodium, linear dodecyl benzene sulfonate triethanolamine, and linear dodecyl benzene sulfonic acid; N-acyl glutamate, such as N-lauroyl glutamate monosodium, N-stearoyl glutamate disodium, and N-myristoyl-L- monosodium glutamate; Higher fatty acid ester sulfate ester salts, such as hydrogenated coconut oil fatty acid glycerol sodium sulfate; Sulfurated oils, such as roast oil; POE-alkyl ether carboxylic acid, POE-alkyl allyl ether carboxylate, α-olefin sulfonate, higher fatty acid ester sulfonate, secondary alcohol sulfate ester, higher fatty acid alkylolamide sulfate ester, lauroyl monoethanol sodium amidosuccinate, N-palmitoyl aspartate ditriethanolamine, sodium caseinate, etc. are mentioned. These anionic surfactants may be used independently and may be used in combination of 2 or more type.

As said cationic surfactant, For example, Alkyl trimethylammonium salts, such as stearyl trimethylammonium chloride and lauryl trimethylammonium chloride; alkylpyridinium salts such as dialkyldimethylammonium salts such as distearyldimethylammonium chloride, poly(N,N'-dimethyl-3,5-methylenepiperidinium chloride), and cetylpyridinium chloride; Alkyl quaternary ammonium salt, alkyldimethylbenzylammonium salt, alkylisoquinolinium salt, dialkylmorpholinium salt, POE-alkylamine, alkylamine salt, polyamine fatty acid derivative, amyl alcohol fatty acid derivative, benzalkonium chloride, benzethonium chloride, etc. can be heard These cationic surfactants may be used independently and may be used in combination of 2 or more type.

Examples of the amphoteric surfactant include 2-undecyl-N,N,N-(hydroxyethylcarboxymethyl)-2-imidazoline sodium and 2-cocoyl-2-imidazolinium hydride. imidazoline-based amphoteric surfactants such as hydroxide-1-carboxyethyloxy disodium salt; Betaine-based surfactants such as 2-heptadecyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, lauryldimethylaminoacetic acid betaine, alkyl betaine, amide betaine, and sulfobetaine; can be heard These amphoteric surfactants may be used independently and may be used in combination of 2 or more type.

As said lipophilic nonionic surfactant, For example, sucrose fatty acid ester; Glycerin fatty acids, such as monocottonseed oil fatty acid glycerol, glycerol monoerucate, glycerol sesquioleate, glycerol monostearate, alpha, (alpha)'- pyroglutamic acid oleate, and glycerol monostearate; polyglycerol fatty acid esters such as diglyceryl monoisostearate and diglyceryl diisostearate; propylene glycol fatty acid esters such as propylene glycol monostearate; Sorbitan monooleate, sorbitan monoisostearate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan sesquioleate, sorbitan trioleate, penta-2-ethylhexyl sorbitan fatty acid esters such as acid diglycerol sorbitan and tetra-2-ethylhexyl acid diglycerol sorbitan; hydrogenated castor oil derivatives, and glycerin alkyl ethers. These lipophilic nonionic surfactants may be used independently and may be used in combination of 2 or more type.

Examples of the hydrophilic nonionic surfactant include POE-sorbitan fatty acid esters such as POE-sorbitan monooleate, POE-sorbitan monostearate, and POE-sorbitan tetraoleate; POE-sorbit fatty acid esters, such as POE-sorbit monolaurate, POE-sorbit monooleate, POE- sorbit pentaoleate, and POE- sorbit monostearate; POE-glycerol fatty acid esters, such as POE-glycerol monostearate, POE-glycerol monoisostearate, and POE-glycerol triisostearate; POE-fatty acid esters, such as POE-monooleate, POE-distearate, POE-dioleate, and POE-stearate; POE-alkyl ethers such as POE-lauryl ether, POE-oleyl ether, POE-stearyl ether, POE-behenyl ether, POE-2-octyldodecyl ether, and POE-cholestanol ether; Pluronic types, such as pluronic; POE·POP-alkyl ethers such as POE·POP-cetyl ether, POE·POP-2-decyltetradecyl ether, POE·POP-monobutyl ether, POE·POP-hydrogenated lanolin, and POE·POP-glycerin ether; tetraPOE·tetraPOP-ethylenediamine polymers such as Tetronic; POE-Hardened Castor Oil, POE-Hardened Castor Oil, POE-Hardened Castor Oil Monoisostearate, POE-Hardened Castor Oil Triisostearate, POE-Hardened Castor Oil Monopyroglutamic Acid Monoisostearate Diester, and POE-Hardened Castor Oil POE-castor oil hydrogenated castor oil derivatives, such as free maleic acid; POE-beeswax-lanolin derivatives, such as POE-sorbit beeswax; alkanolamides such as coconut oil fatty acid diethanolamide, lauric acid monoethanolamide, and fatty acid isopropanolamide; and POE-propylene glycol fatty acid ester, POE-alkylamine, POE-fatty acid amide, sucrose fatty acid ester, POE-nonylphenylformaldehyde polymer, alkylethoxydimethylamine oxide, and trioleyl phosphoric acid. These hydrophilic nonionic surfactants may be used independently and may be used in combination of 2 or more type. In addition, POP is polyoxypropylene.

As said natural surfactant, For example, Lecithins, such as soybean phospholipid, hydrogenated soybean phospholipid, egg yolk phospholipid, and hydrogenated egg yolk phospholipid; and soybean saponins. These natural surfactants may be used independently and may be used in combination of 2 or more type.

Examples of the humectant include polyethylene glycol, propylene glycol, glycerin, 1,3-butylene glycol, xylitol, sorbitol, maltitol, chondroitin sulfate, hyaluronic acid, mucoitin sulfate, caronic acid, atelocollagen, and cholesterol. Steryl-12-hydroxystearate, sodium lactate, urea, bile salt, dl-pyrrolidone carboxylate, short chain soluble collagen, diglycerin ethylene oxide (EO) adduct, diglycerin propylene oxide (PO) adduct water, chestnut glycosylation extract, Yarrow extract, and melilot extract, and the like. These moisturizing agents may be used independently and may be used in combination of 2 or more type.

The thickener includes, for example, gum arabic, carrageenan, gum karaya, gum tragacanth, carob gum, quince seed (quince), casein, dextrin, gelatin, sodium pectate, sodium alginate, methyl cellulose, ethyl cellulose, Carboxymethylcellulose (CMC), hydroxyethylcellulose, hydroxypropylcellulose, polyvinyl alcohol (PVA), polyvinylmethyl ether (PVM), polyvinylpyrrolidone (PVP), sodium polyacrylate, carboxyvinyl polymer, locust Bean gum, guar gum, tamarind gum, dialkyldimethylammonium sulfate cellulose, xanthan gum, aluminum magnesium silicate, bentonite, hectorite, quaternary ammonium salt type cation-modified bentonite, quaternary ammonium salt type cation-modified hectorite and deca A glycerol fatty acid ester eichoic acid diacid condensate etc. are mentioned. These thickeners may be used independently and may be used in combination of 2 or more type.

Examples of the preservative include methylparaben, ethylparaben, and butylparaben. These preservatives may be used independently and may be used in combination of 2 or more type.

As the powder component, for example, talc, kaolin, mica, sericite (sericite), muscovite, phlogopite, synthetic mica, rhodium mica, biotite, lithia mica, vermiculite, magnesium carbonate, calcium carbonate, aluminum silicate, silicic acid Barium, calcium silicate, magnesium silicate, strontium silicate, tungstate metal salt, magnesium, silica, zeolite, barium sulfate, calcined calcium sulfate (bovine gypsum), calcium phosphate, fluorapatite, hydroxyapatite, ceramic powder, metal soap (zinc myristate, calcium palmitate, aluminum stearate), and inorganic powders such as boron nitride; Organic powders such as polyamide resin powder (nylon powder), polyethylene powder, polymethyl methacrylate powder, polystyrene powder, copolymer resin powder of styrene and acrylic acid, benzoguanamine resin powder, polytetrafluoroethylene powder, and cellulose powder and the like. These powder components may be used independently and may be used in combination of 2 or more type.

As the pigment, for example, inorganic white pigments such as titanium dioxide and zinc oxide (titanium dioxide and zinc oxide of particulate type used as ultraviolet scattering agents, or aluminum stearate and zinc palmitate, etc. fatty acid soap, stearic acid, myristic acid, palmitic acid, etc., and a surface-coated inorganic white pigment coated with fatty acid ester such as palmitic acid dextrin); inorganic red pigments such as iron oxide (Bengala) and iron titanate; inorganic brown pigments such as γ-iron oxide; inorganic yellow pigments such as iron sulfate and loess; inorganic black pigments such as black iron oxide, carbon black, and low-order titanium oxide; inorganic purple pigments such as mango violet and cobalt violet; inorganic green pigments such as chromium oxide, chromium hydroxide, and cobalt titanate; Inorganic blue pigments, such as ultramarine blue and royal blue; pearl pigments such as titanium oxide coated mica, titanium oxide coated bismuth oxychloride, titanium oxide coated talc, colored titanium oxide coated mica, bismuth oxychloride, and young leaf; metal powder pigments such as aluminum powder and copper powder; Red No. 201, Red No. 202, Red No. 204, Red No. 205, Red No. 220, Red No. 226, Red No. 228, Red No. 405, Orange No. 203, Orange No. 204, Yellow 205, Yellow No. 401, and Blue Organic pigments such as No. 404, Red No. 3, Red No. 104, Red No. 106, Red No. 227, Red No. 230, Red No. 401, Red No. 505, Orange No. 205, Yellow No. 4, Yellow No. 5, Yellow No. 202 and zirconium such as yellow No. 203, green No. 3 and blue No. 1, and organic pigments such as barium or aluminum lake. These pigments may be used independently and may be used in combination of 2 or more type.

Examples of the pH adjuster include edetic acid, disodium edetic acid, citric acid, sodium citrate, sodium hydroxide, potassium hydroxide, and triethanolamine. These pH adjusters may be used independently and may be used in combination of 2 or more type.

Examples of the antioxidant include vitamin C and their derivatives and their salts, tocopherols and their derivatives and their salts, dibutylhydroxytoluene, butylhydroxyanisole, and gallic acid esters. . These antioxidants may be used independently and may be used in combination of 2 or more type.

Examples of the ultraviolet absorbent include paraaminobenzoic acid (hereinafter, abbreviated as PABA), PABA monoglycerin ester, N,N-dipropoxy PABA ethyl ester, N,N-diethoxy PABA ethyl ester, N, benzoic acid ultraviolet absorbers such as N-dimethyl PABA ethyl ester, N,N-dimethyl PABA butyl ester, and N,N-dimethyl PABA octyl ester; anthranilic acid-based ultraviolet absorbers such as homomenthyl-N-acetylanthranilate; salicylic acid-based ultraviolet absorbers such as amyl salicylate, menthyl salicylate, homomenthyl salicylate, octyl salicylate, phenyl salicylate, benzyl salicylate, and p-isopropanolphenyl salicylate; Octylcinnamate, ethyl-4-isopropylcinnamate, methyl-2,5-diisopropylcinnamate, ethyl-2,4-diisopropylcinnamate, methyl-2,4-diisopropylcinnamate, propyl -p-methoxycinnamate, isopropyl-p-methoxycinnamate, isoamyl-p-methoxycinnamate, octyl-p-methoxycinnamate (2-ethylhexyl-p-methoxycinnamate), 2-ethoxyethyl-p-methoxycinnamate, cyclohexyl-p-methoxycinnamate, ethyl-α-cyano-β-phenylcinnamate, 2-ethylhexyl-α-cyano-β-phenylcinnamate Cinnamic acid ultraviolet absorbers, such as mate and glyceryl mono-2-ethylhexanoyl- diparamethoxycinnamate; 2,4-dihydroxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2', 4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2-hydroxy-4-methoxybenzo Phenone-5-sulfonate, 4-phenylbenzophenone, 2-ethylhexyl-4'-phenyl-benzophenone-2-carboxylate, 2-hydroxy-4-n-octoxybenzophenone, and 4-hydroxy benzophenone-based ultraviolet absorbers such as hydroxy-3-carboxybenzophenone; 3-(4'-methylbenzylidene)-d,l-campa, 3-benzylidene-d,l-campa, urocanic acid, urocanic acid ethyl ester, 2-phenyl-5-methylbenzoxazole, 2 ,2'-hydroxyl-5-methylphenylbenzotriazole, 2-(2'-hydroxyl-5'-t-octylphenyl)benzotriazole, 2-(2'-hydroxyl-5'-methylphenyl)benzo Triazole, dibenzalazine, dianisoylmethane, 4-methoxy-4'-t-butyldibenzoylmethane, 5-(3,3-dimethyl-2-norbornylidene)-3-pentan-2-one and 2,4,6-trianilino-p-(carbo-2'-ethylhexyl-1'-oxy)1,3,5-triazine, 4-tert-butyl-4'-methoxydibenzoyl Methane etc. are mentioned. These ultraviolet absorbers may be used independently and may be used in combination of 2 or more type.

As said pigment|dye, chlorophyll, β-carotene, etc. are mentioned, for example. These dyes may be used independently and may be used in combination of 2 or more type.

Examples of the fragrance include plant fragrances such as rose oil, jasmine oil, and lavender oil, and synthetic fragrances such as limonene, citral, linalool, and eugenol. These perfumes may be used independently and may be used in combination of 2 or more type.

As said sequestering agent, disodium edetate, edetate, hydroxyethane diphosphonic acid, etc. are mentioned, for example. These sequestering agents may be used independently and may be used in combination of 2 or more type.

One aspect of the present invention is a method for moisturizing the skin, comprising applying an effective amount of the composition for external use to the skin comprising the oily moisturizer according to the present invention to the skin surface of a subject in need of moisturizing the skin. The effective amount may be appropriately adjusted depending on the subject to which the external composition for skin is applied and the environment in which the subject is present, but for example, 0.1 mg or more and 20 mg or less per 1 cm 2 of the application site 1 point per 1 time, preferably is 0.2 mg or more and 10 mg or less. In addition, it can be applied 1 or more times and 10 times or less, preferably 1 or more times and 5 times or less per day. In addition, the application period can be adjusted according to the condition of the target. Although continuous use is also possible permanently, application of 1 day to several months, for example, 1 day to 6 months is exemplified. Moreover, single use may be sufficient, and in the case of multiple times of application, application may be sufficient every day, and the non-application day may be included in the period of use.

Evaluation of the moisturizing effect of the external composition for skin can be carried out by applying the composition for external use to the skin in accordance with its usage mode, and evaluating the change in the moisture content of each layer. The moisture content of each layer is evaluated by measuring the electrical conductivity of each layer using a commercially available device. The moisturizing effect of the external composition for skin is evaluated by calculating the change in the moisture content of each layer before and after the test.

Test conditions such as the method of use of the composition for external use for skin, application time, test time, and test period may be determined according to the usage mode of the composition for external use on the skin. In addition, if the composition for external use on the skin, dirt, dust, etc. remain, the electrical conductivity may be affected and the moisture content of each layer may not be accurately evaluated. Therefore, before measuring the electrical conductivity of each layer, they are washed or removed. In addition, it is preferable to carry out evaluation of the moisturizing effect of a skin external composition at a time when skin tends to dry.

More specifically, evaluation of the moisturizing effect at the time of single application of the composition for external use on the skin can be performed, for example, as follows.

First, the electrical conductivity (moisture content of each layer) of each layer of the skin before application of the composition for external use on the skin is measured. Next, after the composition for external use for skin is applied to the skin for a certain period of time according to the usage mode, the composition for external use for skin is removed from the skin surface by washing, wiping, or the like. After a certain period of time has elapsed after removal, the electrical conductivity (moisture content of each layer) of each layer to which the composition for external use has been applied is measured. A moisturizing effect value is calculated using the value of the electrical conductivity (moisture content of each layer) of each layer before and after application of the obtained composition for external use on the skin, and the moisturizing effect is evaluated. In addition, it is preferable to carry out evaluation of the moisturizing effect of a skin external composition at a time when skin tends to dry.

In addition, evaluation of the moisturizing effect at the time of continuous application of the composition for external use on the skin can be performed, for example, as follows.

First, before the start of the continuous test of the composition for external use on the skin, the electrical conductivity of each layer of the skin (the amount of moisture in each layer before the start of the continuous test) is measured. Next, the composition for external use on the skin is applied to the skin at least once a day according to the usage mode, and daily life is performed for several days. On the next day after the end of the continuous test period, the part on which the composition for external use has been applied is washed, the remaining composition for external use on the skin, dirt, dust, etc. are removed, and then the electrical conductivity of each layer (moisture content of each layer at the end of the continuous test) is measured. A moisturizing effect value is calculated using the value of the electrical conductivity (moisture content of each layer) of each layer before and after the obtained continuous test, and the moisturizing effect is evaluated. In addition, it is preferable to carry out evaluation of the moisturizing effect of a skin external composition at a time when skin tends to dry.

As an application example of the composition for external use on skin containing the oily moisturizer according to the present invention, the following are ointment bases, cosmetic oils, water-in-water emulsified cosmetics, sunscreens, water-in-oil emulsified cosmetics, powder cosmetics, hair cosmetics, and emulsified eye makeup cosmetics. , shows a specific aspect of a water-based cosmetic, a solvent-based microfat, a cleaning composition, a pack cosmetic, and an oil-based solid lip cosmetic.

[Ointment base]

In addition to the oil-based moisturizer according to the present invention, the ointment base may contain other oil-based components, oil-based thickeners, antioxidants, and preservatives as appropriate. The content of the oil-based moisturizer according to the present invention in the ointment base is preferably 0.1 to 99 mass%, and the content of the oil-based thickener is preferably 0.1 to 20 mass%.

As an oily moisturizer according to the present invention, for example, a formulation example of an ointment base using an ester product prepared in Example 1 described later, that is, a caprylic acid ester of dipentaerythritol (hydroxyl value 0 mgKOH/g), Table 1 shows. Moreover, as tri(caprylic acid/capric acid) glyceryl, the product "O. D.O" as the palmitic acid dextrin, the product "Leopal KL" manufactured by Chiba Mills Co., Ltd. can be used.

The ointment base of this formulation example 1 can be manufactured by heat-mixing components 1-7 until it melt|dissolves uniformly, pouring into a wide-mouth electric rice cooker container, standing to cool, and cooling.

[Cosmetic Oil]

In addition to the oil-based moisturizer according to the present invention, the cosmetic oil can contain other oil-based components, antioxidants, and preservatives as appropriate. It is preferable that content of the oil-based moisturizer which concerns on this invention in a cosmetic oil is 0.1-100 mass %.

As an oily moisturizer according to the present invention, for example, a formulation example of a cosmetic oil using an esterified product prepared in Example 1 described later, that is, a caprylic acid ester of dipentaerythritol (hydroxyl value 0 mgKOH/g) Table 2 shows.

The cosmetic oil of this formulation example 2 can be manufactured by dissolving components 1-9 and mixing them uniformly.

[Water Type Oil Painting Cosmetics]

In addition to the oil-based moisturizer according to the present invention, the oil-in-water emulsified cosmetic may contain a surfactant, an aqueous moisturizer such as glycerin, a water-soluble polymer, and water. It is preferable that content of the oil-based moisturizer which concerns on this invention in an oil-in-water type emulsion cosmetic is 0.1-60 mass %, It is preferable that content of surfactant is 0.01-10 mass %, Content of an aqueous moisturizer is 1-40 mass % It is preferable that it is mass %, It is preferable that content of a water-soluble polymer is 0.001-5 mass %, It is preferable that content of water is 20-95 mass %.

As an oily moisturizing agent according to the present invention, for example, an esterified product prepared in Example 1 described later, that is, a caprylic acid ester of dipentaerythritol (hydroxyl value 0 mgKOH/g), is used as an oil-in-water type emulsified moisturizing cream. A prescription example is shown in Table 3. Moreover, as dipentaerythrite fatty acid ester, the product "Cosmol 168ARV" by the Nisshin Oilio group company can be used.

The oil-in-water type emulsified moisturizing cream of this formulation example 3 can be manufactured by the following steps A to C. A: The components 1-9 are melt|dissolved by heating and are mixed uniformly. B: Components 10-15 are heated and mixed uniformly. C: At 80°C, the mixture obtained in the step A is added to the mixture obtained in the step B to emulsify, and the component 16 is added after cooling.

An oil-in-water type emulsified hand cream using, for example, an ester product prepared in Example 1 described later, that is, a caprylic acid ester of dipentaerythritol (hydroxyl value 0 mgKOH/g) as an oily moisturizer according to the present invention. A prescription example is shown in Table 4.

The oil-in-water type emulsified hand cream of this formulation example 4 can be manufactured by the following steps A to C. A: Components 1 to 8 are dissolved by heating and mixed uniformly. B: Components 9-13 are heated and mixed uniformly. C: The mixture obtained in step B is added to the mixture obtained in step A at 80°C, emulsified, and cooled.

As an oily moisturizing agent according to the present invention, for example, an in-water type emulsified cleansing cream using an ester product prepared in Example 1 described later, that is, a caprylic acid ester of dipentaerythritol (hydroxyl value 0 mgKOH/g). A prescription example is shown in Table 5.

The oil-in-water type emulsified cleansing cream of this formulation example 5 can be manufactured by the following A-C processes. A: Components 1 to 8 are dissolved by heating and mixed uniformly. B: Components 9-15 are heated and mixed uniformly. C: At 80°C, the mixture obtained in step A is added to the mixture obtained in step B to emulsify, and after cooling, an in-water type emulsified cleansing cream is obtained.

[Sunscreen]

In addition to the oil-based moisturizer according to the present invention, the sunscreen preferably contains a metal oxide powder having an ultraviolet shielding effect, and an organic ultraviolet absorber may be added. When the average particle diameter of the metal oxide powder which has an ultraviolet-ray shielding effect is 10-100 nm, when it apply|coats to skin, since whiteness is suppressed, it is more preferable. It is preferable that content of the oil-based moisturizer which concerns on this invention in a sunscreen is 0.1-60 mass %.

As an oily moisturizing agent according to the present invention, for example, an ester product prepared in Example 1 described later, that is, a caprylic acid ester of dipentaerythritol (hydroxyl value 0 mgKOH/g), and Example 11 described later Table 6 shows a formulation example of a multilayered water-in-oil emulsified sunscreen using the prepared esterified product, that is, a caprylic acid ester of sorbitan (hydroxyl value of 2 mgKOH/g). In addition, as a stearic acid-treated titanium dioxide fine particle, a product "TIPAQUE TTO-S2" manufactured by Ishihara Industrial Co., Ltd., and a product "FINEX 25" manufactured by Sakai Chemical Industries, Ltd. as silicon-treated zinc oxide treated with 5% methylhydrogenpolysiloxane, As cetyldimethicone copolyol, the product "ABIL EM-90" by Evonik company can be used.

The multilayered water-in-oil emulsified sunscreen of this formulation example 6 can be manufactured by the following steps A to D. A: Components 1-13 are mixed uniformly. B: Components 14 to 17 are uniformly mixed. C: The mixture obtained in step B is added to the mixture obtained in step A and emulsified. D: The emulsion obtained in step C is filled in a resin bottle containing stainless steel balls.

As an oily moisturizer according to the present invention, for example, an ester product prepared in Example 1 described later, that is, a caprylic acid ester of dipentaerythritol (hydroxyl value 0 mgKOH/g), is used as a creamy water-type UV protection agent. Table 7 shows the prescription examples of treatment. Moreover, as a stearic acid-treated titanium oxide fine particle, the product "TIPAQUE TTO-S2" by Ishihara Industrial Co., Ltd. can be used.

The creamy water-type sunscreen of this formulation example 7 can be manufactured by the following steps A to E. A: Components 1-10 are heated at 70 degreeC, and are mixed uniformly. B: Components 12-16 are heated at 70 degreeC, and are mixed uniformly. C: The mixture obtained in step B is added to the mixture obtained in step A and emulsified. D: After cooling the emulsion obtained in step C to room temperature, component 11 is added and mixed. E: Fill a container with the mixture obtained in step D.

Formulation example of a water-in-oil sun care cream using, for example, an esterified product prepared in Example 11 described later, i.e., sorbitan caprylic acid ester (hydroxyl value: 2 mgKOH/g), as an oily moisturizer according to the present invention is shown in Table 8. Moreover, the product "KF-6017" by Shin-Etsu Chemical Industries, Ltd. can be used as a polyether-modified silicone, and the product "KF-9021" by Shin-Etsu Chemical Industries, Ltd. can be used as a trimethylsiloxysilicic acid solution.

The water-in-oil sun care cream of this formulation example 8 can be manufactured by the following steps A to C. A: Components 1 to 8 are uniformly mixed at room temperature. B: Components 9 to 12 are uniformly mixed at room temperature. C: The mixture obtained in step B is added to the mixture obtained in step A, and emulsion mixing is performed.

As an oily moisturizer according to the present invention, for example, a formulation example of a stick-type oily concealer using the esterified product prepared in Example 11, that is, sorbitan caprylic acid ester (hydroxyl value of 2 mgKOH/g), Table 9 shows. Further, as a stearic acid-treated titanium oxide, a powder obtained by treating a product "TIPAQUE CR-50" manufactured by Ishihara Industrial Co., Ltd. with 3% by mass of stearic acid as a dipentaerythrit fatty acid ester, a product "Cosmol" manufactured by Nisshin Oilio Group Co., Ltd. 168ARV" can be used.

The stick-shaped oily concealer of this formulation example 9 can be manufactured by the following steps A to D. A: Components 6-14 are heated at 70 degreeC, and are mixed uniformly. B: Components 1 to 5 and component 15 are added to the mixture obtained in step A, and uniformly mixed. C: The mixture obtained in the step B is dissolved again by heating and defoaming. D: The treated material obtained in step C is filled in a stick container and cooled to room temperature.

[Water-in-Oil Emulsifying Cosmetics]

A water-in-oil emulsified cosmetic can be prepared by adding a surfactant and an aqueous component to the oil-based moisturizer according to the present invention. It is preferable that content of the oil-based moisturizer which concerns on this invention in a water-in-oil type emulsion cosmetic is 0.1-60 mass %, It is preferable that content of surfactant is 0.1-10 mass %, Content of an aqueous component is 5-70 It is preferable that it is mass %.

Formulation example of a water-in-oil foundation using, for example, an esterified product prepared in Example 1 described later, that is, a caprylic acid ester of dipentaerythritol (hydroxyl value 0 mgKOH/g) as an oily moisturizer according to the present invention is shown in Table 10. Moreover, the product "KF-6017" by Shin-Etsu Chemical Industries, Ltd. can be used as a polyether-modified silicone, and the product "Benton 38" manufactured by ELEMENTIS can be used as an organic modified clay mineral.

The water-in-oil foundation of this formulation example 10 can be manufactured by the following steps A to C. A: Components 10-17 are heated and mixed, and after cooling to 40 degreeC, components 1-9 and component 18 are added and disperse|distributed with a homomixer. B: Components 19 to 24 are uniformly mixed and dissolved. C: The mixture obtained in step B is added to the dispersion obtained in step A and emulsified.

Prescription of a water-in-oil hand cream using, for example, an esterified product prepared in Example 1 described later, that is, a caprylic acid ester of dipentaerythritol (hydroxyl value 0 mgKOH/g) as an oily moisturizer according to the present invention An example is shown in Table 11. Moreover, as an alkyl containing polyoxyalkylene modified organopolysiloxane, the product "ABIL EM-90" by an Evonik company can be used.

The water-in-oil hand cream of this formulation example 11 can be manufactured by the following steps A to C. A: The components 1-6 are mixed, and the component 7 is disperse|distributed there with a disper mixer. B: Components 8-11 are mixed uniformly. C: The mixture obtained in step B is added to the dispersion obtained in step A and emulsified.

Formulation of a water-in-oil type eye shadow using, for example, an esterified product prepared in Example 2 described later, that is, a caprylic acid ester of dipentaerythritol (hydroxyl value 67 mgKOH/g) as an oily moisturizer according to the present invention An example is shown in Table 12. Moreover, the product "KF-6017" by Shin-Etsu Chemical Industries, Ltd. can be used as a polyether-modified silicone, and the product "KF-7312F" by Shin-Etsu Chemical Industries, Ltd. can be used as a trimethylsiloxysilicic acid solution.

The water-in-oil type eyeshadow of this formulation example 12 can be manufactured by the following steps A to C. A: The components 1-7 are mixed, and the component 8 is disperse|distributed there with a disper mixer. B: Components 9-13 are mixed uniformly. C: The mixture obtained in step B is added to the dispersion obtained in step A and emulsified.

Formulation example of a water-in-oil type mascara using, for example, an esterified product prepared in Example 2 to be described later, that is, a caprylic acid ester of dipentaerythritol (hydroxyl value 67 mgKOH/g) as an oily moisturizer according to the present invention is shown in Table 13. Moreover, as an organic modified clay mineral, the product "Bentone 38" manufactured by ELEMENTIS can be used, and as an organic silicone resin, a product "KF-7312J" manufactured by Shin-Etsu Chemical Industries, Ltd. can be used.

The water-in-oil type mascara of this formulation example 13 can be manufactured by the following steps A to C. A: Components 6-12 are mixed uniformly. B: Components 1 to 5 are uniformly mixed. C: The mixture obtained in step B is added to the mixture obtained in step A and emulsified.

[Powder Cosmetics]

Powder cosmetics contain powders, such as an extender pigment and a coloring pigment, in addition to the oil-based moisturizing agent which concerns on this invention. Preferably, it is preferable that content of the oil-based moisturizer which concerns on this invention in a powder cosmetic is 0.1-30 mass %, It is preferable that content of powder is 70-95 mass %.

Formulation example of a solid powdery foundation using, for example, an esterified product prepared in Example 2 described later, that is, a caprylic acid ester of dipentaerythritol (hydroxyl value 67 mgKOH/g) as an oily moisturizing agent according to the present invention is shown in Table 14.

The solid powdery foundation of this formulation example 14 can be manufactured by the following steps A to D. A: Components 8-12 are heated at 50 degreeC, and are mixed. B: Components 1 to 7 are mixed and dispersed. C: The mixture obtained in step A is added to the mixed dispersion obtained in step B, and mixed. D: The mixture obtained in step C is pulverized and compression molded into a plate.

As an oily moisturizer according to the present invention, for example, a formulation example of a solid powdery white powder using an esterified product prepared in Example 11 to be described later, that is, sorbitan caprylic acid ester (hydroxyl value 2 mgKOH/g) is given in the table. 15 shows. Moreover, as dipentaerythrite fatty acid ester, the product "Cosmol 168ARV" by the Nisshin Oilio group company can be used.

The solid powdery white powder of this formulation example 15 can be manufactured by the following steps A to C. A: Components 1 to 4 are mixed and dispersed. B: Components 5 to 9 are added to the mixed dispersion obtained in step A and mixed uniformly. C: The mixture obtained in step B is pulverized and compression molded into a plate.

A solid powdery cake foundation using, for example, an esterified product prepared in Example 11 to be described later, that is, sorbitan caprylic acid ester (hydroxyl value 0 mgKOH/g) as an oily moisturizing agent according to the present invention (using water) Table 16 shows the prescription examples. Moreover, as a silicone-treated talc, what processed 5 mass % of methylhydrogenpolysiloxane of a talc and what processed 5 mass % of perfluoroalkyl phosphate diethanolamine salts can be used as a fluorine-treated sericite.

The solid powdery cake foundation (using water) of this formulation example 16 can be manufactured by the following steps A to D. A: Components 1 to 8 are mixed and dispersed. B: Components 9-13 are heated at 50 degreeC, and are mixed. C: The mixture obtained in step B and component 14 are added to the mixed dispersion obtained in step A, and mixed uniformly. D: The mixture obtained in step C is pulverized and compression molded into a plate.

A table of formulation examples of powdered rouge using, for example, an esterified product prepared in Example 11 described later, that is, a sorbitan caprylic acid ester (hydroxyl value of 2 mgKOH/g) as an oily moisturizer according to the present invention. 17 shows.

The powdery cheek rouge of this formulation example 17 can be manufactured by the following steps A to C. A: Components 1 to 6 are uniformly mixed and dispersed. B: Component 7 is added to the mixed dispersion obtained in step A and mixed uniformly. C: The mixture obtained in step B is grind|pulverized, and it fills in a container.

As an oily moisturizing agent according to the present invention, for example, an esterified product prepared in Example 11 described later, that is, a caprylic acid ester of sorbitan (hydroxyl value of 2 mgKOH/g) is used as a formulation example of a powdery eye color. 18 shows.

The powdery eye color of this formulation example 18 can be manufactured by the following steps A to C. A: Components 1 to 6 are uniformly mixed and dispersed. B: Component 7 is added to the mixed dispersion obtained in step A and mixed uniformly. C: The mixture obtained in step B is grind|pulverized, and it fills in a container.

As an oily moisturizer according to the present invention, for example, an esterified product prepared in Example 11 to be described later, that is, a sorbitan caprylic acid ester (hydroxyl value of 2 mgKOH/g) is used as a formulation example of a powdered body powder. 19 is shown.

The powdery body powder of this formulation example 19 can be manufactured by the following steps A to C. A: Components 1 to 4 are uniformly mixed and dispersed. B: Component 5 is added to the mixed dispersion obtained in step A and mixed uniformly. C: The mixture obtained in step B is grind|pulverized, and it fills in a container.

[Hair Cosmetics]

The hair cosmetic contains a cationic surfactant in addition to the oil-based moisturizer according to the present invention. The hair cosmetic can be prepared by further adding a higher alcohol, water, a moisturizing agent, or the like.

Table 20 shows a formulation example of a hair cream using, for example, an esterified product prepared in Example 11 to be described later, that is, sorbitan caprylic acid ester (hydroxyl value: 2 mgKOH/g) as an oily moisturizer according to the present invention. is shown in Further, as dimethylpolysiloxane, product "KF96A (6cs)" manufactured by Shin-Etsu Chemical Industry Co., Ltd., product "GENAMIN STAC" manufactured by Clariant Japan, as stearyltrimethylammonium chloride, as polyoxyethylene oleyl ether, as polyoxyethylene oleyl ether, Nippon Emulsion The product "EMALEX 503" manufactured by the company can be used.

The hair cream of this formulation example 20 can be manufactured by the following steps A to C. A: Components 1 to 6 are uniformly mixed and dissolved. B: Components 7-11 and 13 are uniformly mixed and dissolved. C: The mixture obtained in step B is added to the mixture obtained in step A at 80°C, and after emulsification, component 12 is added and cooled.

As an oily moisturizer according to the present invention, for example, a formulation example of a hair conditioner using an ester product prepared in Example 2 described later, that is, a caprylic acid ester of dipentaerythritol (hydroxyl value of 67 mgKOH/g). Table 21 shows.

The hair conditioner of this formulation example 21 can be manufactured by the following steps A to C. A: The components 1-6 are melt|dissolved and mixed uniformly. B: The components 7-11 are melt|dissolved and mixed uniformly. C: After emulsifying while adding the mixture obtained in step A to the mixture obtained in step B at 80°C, component 12 is added and mixed.

As an oily moisturizer according to the present invention, for example, a hair rinse (for washing off) using an esterified product prepared in Example 2 described later, that is, a caprylic acid ester of dipentaerythritol (hydroxyl value of 67 mgKOH/g). ) is shown in Table 22. Moreover, as a highly polymerized methylpolysiloxane emulsion, the product "BY22-073" by Toray Dow Corning can be used.

The hair conditioner (for washing off) of this formulation example 22 can be manufactured by the following steps A to C. A: Components 1 to 4 are uniformly dissolved and mixed. B: Components 5 to 9 are uniformly dissolved and mixed. C: After emulsifying while adding the mixture obtained in step A to the mixture obtained in step B at 80°C, component 10 is added and mixed.

As an oily moisturizer according to the present invention, for example, an esterified product prepared in Example 16 described later, that is, a (caprylic acid/capric acid) ester of erythritol (caprylic acid and capric acid composition ratio of constituent fatty acid residues) Table 23 shows a formulation example of a cuticle protective gel using 80:20 and a hydroxyl value of 9 mgKOH/g).

The cuticle protective gel of this formulation example 23 can be manufactured by the following steps A to D. A: Components 1 to 5 are uniformly mixed. B: Components 6-11 are mixed uniformly. C: It mixes and disperse|distributes adding the mixture obtained by A process to the mixture obtained by B process. D: To the mixture obtained in step C, component 12 is added and uniformly mixed.

[Oil type Eye Makeup Cosmetics]

The emulsified eye makeup cosmetic contains a film-forming polymer emulsion in addition to the oil-based moisturizer according to the present invention. The emulsified eye makeup cosmetic can be prepared by adding the oil-based moisturizer and the film-forming polymer emulsion according to the present invention, and further adding a surfactant, a pigment, a higher alcohol, water, a moisturizing agent, and the like. It is preferable that content of the oil-based moisturizer which concerns on this invention in an emulsion type eye makeup cosmetic is 0.1-80 mass % in emulsion type eye makeup cosmetic whole quantity. Moreover, as said emulsion type eye makeup cosmetic, it is preferable that solid content in a film-forming polymer emulsion is 0.1-30 mass % in emulsion type eye makeup cosmetic whole quantity.

As an oily moisturizer according to the present invention, for example, an ester product prepared in Example 11 described later, that is, a caprylic acid ester of sorbitan (hydroxyl value of 2 mgKOH/g), and an ester product prepared in Example 16 described later An esterified product, that is, a (caprylic acid/capric acid) ester of erythritol (caprylic acid and capric acid composition ratio of the constituent fatty acid residues of 80:20, hydroxyl value of 9 mgKOH/g) is used as an emulsified type Table 24 shows the formulation examples of mascara.

The oil-in-water type emulsion type mascara of this formulation example 24 can be manufactured by the following steps A to D. A: The components 1-9 are heat-dissolved, the components 10-12 are added, and it mixes uniformly. B: Components 13 to 21 are uniformly mixed. C: The mixture obtained in step B is added to the mixture obtained in step A and emulsified. D: Fill a container with the mixture obtained in step C.

As an oily moisturizer according to the present invention, for example, an esterified product prepared in Example 16 described later, that is, a (caprylic acid/capric acid) ester of erythritol (caprylic acid and capric acid composition ratio of constituent fatty acid residues) Table 25 shows a formulation example of a water-in-oil emulsified mascara using 80:20 and a hydroxyl value of 9 mgKOH/g).

The water-in-oil emulsified mascara of this formulation example 25 can be manufactured by the following steps A to D. A: Heat-dissolve components 1-5, and mix uniformly. B: Components 6-11 are mixed uniformly. C: The mixture obtained in step B is added to the mixture obtained in step A and emulsified. D: Fill a container with the mixture obtained in step C.

As an oily moisturizer according to the present invention, for example, an ester product prepared in Example 6 described later, that is, a (caprylic/capric acid) ester of dipentaerythritol (caprylic acid and capric acid of constituent fatty acid residues) Table 26 shows a formulation example of an oil-in-water emulsion type eyeliner using an acid composition ratio of 80:20 and a hydroxyl value of 150 mgKOH/g).

The oil-in-water type emulsion type eyeliner of this formulation example 26 can be manufactured by the following steps A to D. A: The components 1-4 are heat-dissolved, the components 5 and 6 are added, and it mixes uniformly. B: Components 7 to 13 are uniformly mixed. C: The mixture obtained in step B is added to the mixture obtained in step A and emulsified. D: Fill a container with the mixture obtained in step C.

Prescription of an oil-in-water type emulsified eyeshadow using, for example, an esterified product prepared in Example 11 described later, i.e., sorbitan caprylic acid ester (hydroxyl value: 2 mgKOH/g), as the oil-based moisturizer according to the present invention An example is shown in Table 27.

The oil-in-water type emulsion type eyeshadow of this formulation example 27 can be manufactured by the following steps A to D. A: The components 1-6 are heat-dissolved, the components 7 and 8 are added, and it mixes uniformly. B: Components 9-16 are mixed uniformly. C: The mixture obtained in step B is added to the mixture obtained in step A and emulsified. D: Fill a container with the mixture obtained in step C.

Prescription of an in-water type emulsified eyebrow using, for example, an esterified product prepared in Example 11 described later, that is, sorbitan caprylic acid ester (hydroxyl value 2 mgKOH/g) as an oily moisturizer according to the present invention An example is shown in Table 28.

The oil-in-water type emulsion type eyebrow of this formulation example 28 can be manufactured by the following steps A to D. A: The components 1-6 are heat-dissolved, the component 7 is added, and it mixes uniformly. B: Components 8-13 are mixed uniformly. C: The mixture obtained in step B is added to the mixture obtained in step A and emulsified. D: Fill a container with the mixture obtained in step C.

[Water-based cosmetics]

The water-based cosmetic contains ethanol, a nonionic surfactant, an alkyl-modified carboxyvinyl polymer, and water in addition to the oil-based moisturizer according to the present invention. It is preferable that content of the oil-based moisturizer which concerns on this invention in a water-based cosmetic is 0.01-40 mass % in water-based cosmetic whole quantity.

As an oily moisturizer according to the present invention, for example, an ester product prepared in Example 6 described later, that is, a (caprylic/capric acid) ester of dipentaerythritol (caprylic acid and capric acid of constituent fatty acid residues) Table 29 shows formulation examples of lotions using an acid composition ratio of 80:20 and a hydroxyl value of 150 mgKOH/g).

The lotion of this formulation example 29 can be manufactured by the following steps A to C. A: Components 1 to 3 are uniformly mixed and dissolved. B: Components 4 to 8 are uniformly mixed and dissolved. C: The mixture obtained in step A is added to the mixture obtained in step B while stirring, and a container is filled.

As an oily moisturizer according to the present invention, for example, an ester product prepared in Example 6 described later, that is, a (caprylic/capric acid) ester of dipentaerythritol (caprylic acid and capric acid of constituent fatty acid residues) Table 30 shows formulation examples of cosmetic solutions using an acid composition ratio of 80:20 and a hydroxyl value of 150 mgKOH/g).

The cosmetic liquid of this formulation example 30 can be manufactured by the following steps A to C. A: Components 1 to 5 are uniformly mixed and dissolved. B: Components 6-11 are uniformly mixed and dissolved. C: The mixture obtained in step A is added to the mixture obtained in step B while stirring, and a container is filled.

As an oily moisturizer according to the present invention, for example, an ester product prepared in Example 6 described later, that is, a (caprylic/capric acid) ester of dipentaerythritol (caprylic acid and capric acid of constituent fatty acid residues) Table 31 shows a formulation example of a gel eye color using an acid composition ratio of 80:20 and a hydroxyl value of 150 mgKOH/g).

The gel eye color of this formulation example 31 can be manufactured by the following steps A to C. A: Components 1 to 7 are uniformly mixed and dissolved. B: Components 8 to 11 are uniformly mixed and dissolved. C: Add to the mixture obtained in step B while stirring the mixture obtained in step A.

[Solvent-based non-seasoning]

In addition to the oil-based moisturizer according to the present invention, the solvent-based microfat contains a film-forming agent and a non-aromatic solvent. It is preferable that content of the oil-based moisturizer which concerns on this invention in a solvent-type microfat is 0.01-40 mass % in the total amount of a solvent-type microfat.

As an oily moisturizer according to the present invention, for example, an ester product prepared in Example 5 described later, that is, a (caprylic acid/capric acid) ester of dipentaerythritol (caprylic acid and capric acid residues of constituent fatty acid residues) Table 32 shows formulation examples of nail polish using an acid composition ratio of 80:20 and a hydroxyl value of 0 mgKOH/g). Further, as the alkyl acrylate/styrene copolymer, the product "Acrybase MH7057" by Fujikura Chemical Co., Ltd., as the organic modified clay mineral, "Benton 27" by ELEMENTIS, as silicic anhydride, was Nippon Aero A product "AEROSIL 300" manufactured by Zilsa can be used.

The nail polish of this formulation example 32 can be manufactured by the following steps A to C. A: The components 7-9 are mixed, the component 10 is added, and it mixes uniformly. B: Components 1 to 6 are added to the mixture obtained in step A and mixed uniformly. C: Components 11 to 15 are added to the mixture obtained in step B, mixed uniformly, and a container is filled.

As an oily moisturizer according to the present invention, for example, an ester product prepared in Example 5 described later, that is, a (caprylic acid/capric acid) ester of dipentaerythritol (caprylic acid and capric acid residues of constituent fatty acid residues) Table 33 shows a formulation example of a top coat using an acid composition ratio of 80:20 and a hydroxyl value of 0 mgKOH/g). Moreover, as an alkyl acrylate styrene copolymer, the product "Acrybase MH7057" by a Fujikura Chemical Company can be used.

The top coat of this formulation example 33 can be manufactured by the following steps A to B. A: After mixing components 5-8 uniformly, components 1-4 are added and it mixes uniformly. B: The mixture obtained in step A is filled in a container.

As an oily moisturizer according to the present invention, for example, an ester product prepared in Example 5 described later, that is, a (caprylic acid/capric acid) ester of dipentaerythritol (caprylic acid and capric acid residues of constituent fatty acid residues) Table 34 shows a formulation example of a base coat using an acid composition ratio of 80:20 and a hydroxyl value of 0 mgKOH/g). Moreover, as an alkyl acrylate styrene copolymer, the product "Acrybase MH7057" by a Fujikura Chemical Company can be used.

The base coat of this formulation example 34 can be manufactured by the following steps A to B. A: After mixing components 4-7 uniformly, components 1-3 are added and it mixes uniformly. B: The mixture obtained in step A is filled in a container.

[Cleaning agent composition]

In addition to the oily moisturizer which concerns on this invention, a cleaning composition contains 1 type(s) or 2 or more types chosen from anionic surfactant, an amphoteric surfactant, and a nonionic surfactant. It is preferable that content of the oil-based moisturizer which concerns on this invention in a cleaning composition is 0.01-30 mass % in cleaning composition whole quantity. It is preferable that the 1 type(s) or 2 or more types of total content chosen from the anionic surfactant in a detergent composition, an amphoteric surfactant, and a nonionic surfactant is 0.01-40 mass % in the detergent composition whole quantity.

As an oily moisturizer according to the present invention, for example, an ester product prepared in Example 5 described later, that is, a (caprylic acid/capric acid) ester of dipentaerythritol (caprylic acid and capric acid residues of constituent fatty acid residues) Table 35 shows formulation examples of shampoos using an acid composition ratio of 80:20 and a hydroxyl value of 0 mgKOH/g).

The shampoo of this formulation example 35 can be manufactured by mixing components 1-9 uniformly.

As an oily moisturizer according to the present invention, for example, an ester product prepared in Example 5 described later, that is, a (caprylic acid/capric acid) ester of dipentaerythritol (caprylic acid and capric acid residues of constituent fatty acid residues) Table 36 shows a formulation example of a body soap using an acid composition ratio of 80:20 and a hydroxyl value of 0 mgKOH/g).

The body soap of this formulation example 36 can be manufactured by mixing components 1-10 uniformly.

As an oily moisturizer according to the present invention, for example, an ester product prepared in Example 5 described later, that is, a (caprylic acid/capric acid) ester of dipentaerythritol (caprylic acid and capric acid residues of constituent fatty acid residues) Table 37 shows a formulation example of a face wash using an acid composition ratio of 80:20 and a hydroxyl value of 0 mgKOH/g). Moreover, the product "KF-96H-6000cs" manufactured by Shin-Etsu Chemical Industry Co., Ltd. can be used as the highly polymerized dimethylpolysiloxane.

The face cream of this formulation example 37 can be manufactured by the following steps A to C. A: The components 1-7 are heat-dissolved and it shall be 70 degreeC. B: The components 8-12 are heated to 70 degreeC. C: It is gradually added to the mixture obtained in the step B at 70°C while stirring the mixture obtained in the step A, and after the saponification reaction is completed, the mixture is cooled while stirring.

Formulation example of a gel face wash using, for example, an ester product prepared in Example 1 described later, that is, a caprylic acid ester of dipentaerythritol (hydroxyl value 0 mgKOH/g) as an oily moisturizer according to the present invention is shown in Table 38.

The gel face wash of this formulation example 38 can be manufactured by the following steps A to B. A: Components 1-3 are mixed uniformly. B: Components 4 to 9 are added to the mixture obtained in step A and mixed uniformly.

As the oily moisturizing agent according to the present invention, for example, the ester product prepared in Example 1 described later, that is, the caprylic acid ester of dipentaerythritol (hydroxyl value 0 mgKOH/g), the ester prepared in Example 11 The product, that is, the caprylic acid ester of sorbitan (hydroxyl value: 2 mgKOH/g), and the ester product prepared in Example 15, that is, the caprylic acid ester of erythritol (hydroxyl value: 0 mgKOH/g) Table 39 shows the formulation examples of the cleansing oil used.

The cleansing oil of this formulation example 39 can be manufactured by mixing components 1-9 uniformly.

[Pack Cosmetics]

The pack cosmetic can contain, in addition to the oil-based moisturizer according to the present invention, an aqueous moisturizer such as glycerin, a water-soluble polymer, and water. It is preferable that content of the oil-based moisturizer which concerns on this invention in pack cosmetics is 0.1-60 mass %, It is preferable that content of an aqueous moisturizer is 1-40 mass %, Content of a water-soluble polymer is 0.001-20 mass % It is preferable that it is, and, as for content of water, it is preferable that it is 20-95 mass %.

As an oily moisturizer according to the present invention, for example, a paste-like peel of pack using an ester product prepared in Example 1 described later, that is, a caprylic acid ester of dipentaerythritol (hydroxyl value 0 mgKOH/g). A prescription example is shown in Table 40. Moreover, as polyvinyl alcohol, the product "Kurarepoval PVA217" by a Kuraray company can be used.

The paste-like peel of pack of this formulation example 40 can be manufactured by the following steps A to C. A: Components 1 to 5 are uniformly mixed. B: Components 6 to 9 are uniformly mixed. C: The mixture obtained in the step B is added to the mixture obtained in the step A, the mixture is heated and stirred at 50°C, and the component 10 is added after cooling.

As an oily moisturizing agent according to the present invention, for example, a formulation example of a cream pack using an ester product prepared in Example 1 described later, that is, a caprylic acid ester of dipentaerythritol (hydroxyl value 0 mgKOH/g) Table 41 shows.

The cream pack of this formulation example 41 can be manufactured by the following steps A to C. A: The components 1-6 are heated and melt|dissolved at 80 degreeC, and it mixes uniformly. B: Components 7-12 are heated and dissolved at 80 degreeC, and are mixed uniformly. C: The mixture obtained in step B is added to the mixture obtained in step A at 80° C., emulsified, cooled, and component 13 is added.

Formulation example of a sheet pack using, for example, an esterified product prepared in Example 1 described later, that is, a caprylic acid ester of dipentaerythritol (hydroxyl value 0 mgKOH/g) as an oily moisturizing agent according to the present invention is shown in Table 42. In addition, as the monooleate polyglyceryl-10, a product "Saracos PG-180" manufactured by Nisshin Oilio Group Co., Ltd. and "Saracos DG-180" manufactured by the Nisshin Oilio group company as monooleate polyglyceryl-2 may be used as the monooleate polyglyceryl-10. can

The sheet-like pack of this formulation example 42 can be manufactured by the following steps A to D. A: Components 1 to 3 are dissolved by heating and mixed uniformly. B: Components 4 to 9 are heated and mixed uniformly. C: The mixture obtained in the step A is added to the mixture obtained in the step B, emulsified, and the liquid part for a sheet-like pack is obtained. D: The nonwoven fabric is impregnated with the liquid part obtained in the step C to obtain a sheet-like pack.

[oily solid lip cosmetics]

The oil-based solid lip cosmetic can contain, in addition to the oil-based moisturizer according to the present invention, a wax component having a melting point of 70°C or higher, other oil-based components, organic pigments, inorganic pigments, antioxidants, and preservatives as appropriate. It is preferable that content of the oil-based moisturizer which concerns on this invention in a cosmetic oil is 0.1-95 mass %.

Prescription of an oily solid lip cosmetic using, for example, an esterified product prepared in Example 1 to be described later, that is, a caprylic acid ester of dipentaerythritol (hydroxyl value 0 mgKOH/g) as an oily moisturizer according to the present invention An example is shown in Table 43.

In addition, as dipentaerythrit fatty acid ester, product "Cosmol 168ARV" manufactured by Nisshin Oilio Group Co., Ltd., and as tripolyhydroxystearate dipentaerythrityl, product "Saracos WO-6" manufactured by Nisshin Oilio Group Ltd. , As triisostearate polyglyceryl-2, the product "Cosmol 43V" manufactured by Nisshin Oilio Group can be used.

The oily solid lip cosmetic of this formulation example 43 can be manufactured by the following steps A to D. A: Components 5-16 are heated at 90 degreeC, and are mixed uniformly. B: Components 1 to 4 and component 17 are added to the mixture obtained in step A, and uniformly mixed. C: The mixture obtained in the step B is dissolved again by heating and defoaming. D: The treated material obtained in step C is filled in a stick container and cooled to room temperature.

Example

Hereinafter, although it demonstrates in more detail based on the Example of this invention, this invention is not limited at all to these description. In addition, in the following, unless otherwise indicated, "%" means mass %.

[Examples 1 to 18, Comparative Examples 1 to 9] Preparation of esterified products

Alcohol and fatty acid were used as reaction raw materials, the molar ratio of alcohol and fatty acid was adjusted, the esterification reaction was performed, and the esterification product was manufactured.

Specifically, first, the alcohols and fatty acids shown in Tables 46 and 47 are poured into a four-necked flask, heated to 180 to 240° C. under a nitrogen stream, and esterified for about 10 to 20 hours while removing the water generated outside the system. The reaction was carried out. After completion of the reaction, excess acid was removed as needed to obtain the target esterified product.

More specifically, the esterified product of Example 5 was produced by the method shown in Production Example 1 described later. In addition, the esterified product of Example 2 was manufactured by the method shown to the manufacture example 2 mentioned later.

Tables 46 and 47 show the result of evaluation of the properties (appearance) of the obtained esterified product, the hydroxyl value, the properties (appearance) at 35°C, the moisturizing effect, and the feeling of use.

Moreover, about the esterified material manufactured using two types of fatty acids as a raw material, the composition of the constituent fatty acid residues of the obtained esterified material was measured, and the mass ratio of each constituent fatty acid residue was computed. The values are shown in Tables 46 and 47.

[Production Example 1] Preparation of esterified product

Using dipentaerythritol, caprylic acid, and capric acid as reaction raw materials, the hydroxyl value of the resulting esterified product is 0 mgKOH/g, and the mass ratio of caprylic and capric acid of the resulting esterified product is 8:2. The esterification reaction was carried out by adjusting the molar ratio of dipentaerythritol, caprylic acid, and capric acid to prepare an esterified product.

Specifically, 1198.6 g (8.3 mol) of caprylic acid, 299.6 g (1.7 mol) of capric acid, and 254.3 g (1.0 mol) of dipentaerythritol were first poured into a four-necked flask, and under a nitrogen stream, 230 to The esterification reaction was performed for about 15 hours while heating to 240 degreeC and removing the water produced|generated out of the system. After completion of the reaction, the excess acid was removed to obtain 940 g of the target esterified product.

The acid value of the obtained esterified product was 0.1, and the hydroxyl value was 0 mgKOH/g.

In addition, the mass ratio of the constituent fatty acid residues of the obtained esterified product was caprylic acid:capric acid = 79:21.

[Preparation Example 2] Preparation of esterified product

Using dipentaerythritol and caprylic acid as reaction raw materials, the esterification reaction is carried out by adjusting the molar ratio of dipentaerythritol and caprylic acid so that the hydroxyl value of the resulting esterified product is about 70 mgKOH/g, cargo was manufactured.

Specifically, first, 692.2 g (4.8 mol) of caprylic acid and 254.3 g (1.0 mol) of dipentaerythritol are poured into a four-necked flask, heated to 230 to 240° C. under a nitrogen stream, and the resulting water is The esterification reaction was carried out for about 25 hours while being removed from the system. When it was confirmed that the acid value of the reactant became less than 1, the reaction was completed, and 817 g of the target esterified product was obtained. The obtained esterified product had an acid value of 0.1 and a hydroxyl value of 67 mgKOH/g.

[Comparative Example 10] Preparation of dipentaerythritol fatty acid ester

Using dipentaerythritol and caprylic acid as reaction raw materials, the esterification reaction was carried out by adjusting the molar ratio of dipentaerythritol and caprylic acid so that the hydroxyl value of the resulting esterified product was about 170 mgKOH/g. It separated into two phases in the middle, and the target esterified product could not be produced.

Therefore, various evaluations of dipentaerythritol fatty acid ester having a hydroxyl value of about 170 mgKOH/g could not be performed.

<Measurement of composition of constituent fatty acid residues of esterified products>

In the following examples, etc., the mass ratio of each constituent fatty acid residue of the esterified product is the fatty acid residue in the esterified product, 2.4.1.1-2013 methyl esterification method (sulfuric acid-methanol method) (published by the Japan Oil Chemical Society, a public interest corporation, " After preparing a methyl esterified derivative by a method corresponding to the "Test Method for Oil Analysis Test Method 2013" established by the Japan Oil Chemical Society, 2.4.2.3-2013 fatty acid composition (capillary gas chromatography method) ( It was separated and measured by a method equivalent to the "Japan Oil Chemical Society Establishment Standard Oil and Oil Analysis Test Method 2013 Edition") published by the Japan Oil Chemical Society, a public interest corporation.

Specifically, first, 1 drop of the esterified product was aliquoted into a test tube and dissolved in 2 ml of a sulfuric acid-methanol solution [a solution of 230 ml of methanol mixed with 2 ml of sulfuric acid]. Next, the test tube was heated to prepare a derivative obtained by methyl esterification of the fatty acid residue in the esterified product by transesterification.

This methyl ester derivative was dissolved in 2 ml of hexane, poured into a column of a gas chromatograph equipped with FID, and each methyl ester derivative was separated and detected under the following GC analysis conditions.

<GC analysis conditions>

·Column: DB-1ht (manufactured by Agilent Technologies)

・Injection amount: 1 μl

·Carrier gas: Helium

·Column temperature: 50 ~ 370 ℃ (temperature rise 15 ℃/min)

Identification of the peak on the chromatograph was performed by comparing the retention time of the peak obtained by analyzing a standard substance under the same measurement conditions as the test sample. The composition of the fatty acid residue of the esterified product was calculated based on the percentage (%) of the peak area of the peak of the methyl ester derivative derived from each fatty acid residue on the chromatograph.

<Test for measuring moisture content in each layer of the skin>

In the present invention, the moisturizing effect of the esterified product, that is, the improvement effect of the skin moisturizing function, was evaluated based on the change in the amount of moisture in each layer of the skin before and after the application of the esterified product.

The moisture content in each layer was measured using a moisture content measuring device in each layer (device name: SKICON-200) manufactured by IBS. The moisture content measuring apparatus of each layer is an apparatus used for general purpose in order to measure the moisture state of each layer, and is an apparatus for measuring the electrical conductivity (µS) of each layer. The higher the skin moisture content, the higher the electrical conductivity of each layer. Therefore, the electrical conductivity (μS) measured by the moisture content measuring device of each layer was taken as the moisture content of each layer.

<Evaluation test for moisturizing effect at the time of single application of an esterified product>

The skin moisturizing effect of the test sample was evaluated based on the amount of change in the amount of moisture in each layer of the skin after the test sample was directly applied to the washed skin and then wiped with a cotton swab soaked in hexane.

The moisture content measurement test of each layer of the skin was conducted for a plurality of panelists during the period when the skin tends to dry from autumn to spring. Moreover, in order to eliminate the influence of room temperature and humidity with respect to a measurement result, the test was implemented in the room which adjusted room temperature to 18-22 degreeC and humidity to 40-55 %RH.

Specifically, first, the human forearm is washed with soap, and then the skin of the forearm is acclimatized to the measurement environment by staying in the room adjusted to the room temperature and humidity in the above ranges for 30 minutes, and the initial stage of the measurement Conditions were arranged.

Next, a 3 cm long and 3 cm wide square of the washed forearm was used as a measurement site, and the moisture content of each layer of the skin in that part was measured, and it was set as a blank value (moisture content of each layer before the start of the test).

Thereafter, 40 µL of the test sample to be evaluated was uniformly applied to the square measurement site of the forearm. 60 minutes after application, the test sample was wiped off with a cotton swab impregnated with hexane, and 30 minutes after wiping, the moisture content of each layer of the skin of the wiped area (moisture content of each layer at the end of the test) was measured.

In addition, in evaluating the moisturizing effect of the test sample, in order to take into account the change in the skin condition within the measurement time and subtract this, the moisture content of each layer of the sample uncoated part is also measured before the start of the test and at the end of the test, and the moisture content of each layer of the uncoated part change was calculated.

From the measured value of the measured amount of moisture in each layer of skin, a moisturizing effect value (µS) was calculated based on the following formula. The moisturizing effect value (µS) of each test sample was taken as the average value of the moisturizing effect value (µS) of five panelists.

(Equation 1) [Moisturizing effect value (μS)] = [Moisture content in each layer of the applied part (μS) at the end of the test] - [Moisture amount in each layer of the blank (μS)] - [Amount of moisture in each layer of the uncoated part (μS)] (Equation 2 ) [Amount of moisture in each layer in the uncoated part (μS)] = [Moisture content in each layer in the uncoated part (μS) at the end of the test] - [Moisture content in each layer in the uncoated part (μS) before the start of the test]

Based on the moisturizing effect value (µS) of each test sample, the moisturizing effect of each test sample was evaluated according to the criteria in Table 44. The test samples with moisturizing evaluations a1, b1, and c1 had a moisturizing effect and were judged to be useful as a moisturizer, and the test samples for d1 and e1 did not have a sufficient moisturizing effect and were judged not to be useful as a moisturizer.

<Evaluation of moisturization at the time of single application>

About each esterified product, the said <moisturizing effect evaluation test at the time of single application|coating of an esterified product> was implemented by 5 panelists, and moisturizing evaluation was performed.

However, since the epidermal temperature of the skin at the time of a test is about 30-35 degreeC, the evaluation sample of a solid phase at 35 degreeC cannot apply|coat well to skin. Therefore, with respect to the esterified product in a solid state at 35°C, it was mixed with cetyl 2-ethylhexanoate (trade name “Saracos 816T”, manufactured by Nisshin Oilio Group Co., Ltd.) in a mass ratio of 1:1, and became liquid at 35°C. It was set as the blank sample for evaluation.

<Evaluation of usability>

In a composition for external use on the skin, it is also important for practical use that the feeling of use is excellent. Sensory evaluation was performed on each esterified product for feeling of use, specifically, “no stickiness” and “adhesion”.

By 4 expert evaluation panelists, 5 levels (5 points: good, 4 points: slightly Good, 3 points: average, 2 points: slightly bad, 1 point: bad). The evaluation point of the feeling of use of each test sample was made into the average value of the evaluation point of 4 panelists.

Based on the evaluation point of "no stickiness" of each test sample, the usability of each test sample was evaluated by the criteria of Table 45.

Based on the evaluation point of "adhesion feeling" of each test sample, the usability|use_condition of each test sample was evaluated by the reference|standard of Table 46.

[Comparative Examples 11 to 23]

For various commercially available oil agents and glycerin, the above <evaluation of moisturizing at the time of single application> was performed to investigate the moisturizing effect. Table 49 shows the properties (appearance) and evaluation results of various commercially available oil agents and glycerin at 35°C.

Glycerin of Comparative Example 23 is a representative substance of an aqueous moisturizer, and is generally used as a moisturizer. In the case of glycerin, a cotton swab moistened with water, not hexane, was used to remove the glycerin applied to the skin in the above <Evaluation of moisture in single application>. Evaluation conditions except that the solvent to be removed was changed from hexane to water were the same as those of <Evaluation of moisture retention at the time of single application>.

From the results in Tables 47 to 49, dipentaerythritol, erythritol, or sorbitan was used as an alcohol as the reaction raw material for the esterification products of Examples 1 to 18, ie, esterification reaction, and 6 to 28 carbon atoms as fatty acids. An esterified product having a hydroxyl value of 0 to 160 mgKOH/g obtained by necessarily using one or two or more fatty acids selected from fatty acids of found it to be very useful. On the other hand, although dipentaerythritol, erythritol, and sorbitan are esterified products of Comparative Examples 2 to 5, 8 and 9 in which none of the raw materials are used as raw materials, erythritol or dipentaerythritol are used as raw materials; The esterified product of Comparative Example 1, wherein the mass ratio of the fatty acid residue derived from component B to the fatty acid residue derived from component C in the fatty acid residue constituting the esterified product of component C is outside the range of 99.9:0.1 to 45:55, and erythritol was used as a raw material, but the esterified products of Comparative Examples 6 and 7 which did not use component B as a raw material had a moisturizing effect value of less than 50 µS, and a sufficient moisturizing effect as a moisturizing agent was not observed. The oil agents of Comparative Examples 11 to 22 are oil agents that have been conventionally used as raw materials for external composition for skin. has been confirmed to exert

The esterified products of Examples 1 to 18 were able to maintain a high moisture content in each layer even after being removed from the skin. In this regard, it is presumed that the moisturizing effect is exhibited by a mechanism different from that of the conventional oil-based moisturizer which exhibits a moisturizing effect by suppressing evaporation of water from the skin by attaching an oily film to the skin surface.

Although the glycerin of Comparative Example 23 has generally good moisturizing properties and is widely used as an aqueous moisturizer, in this moisturizing evaluation result, the moisturizing effect value of glycerin was 8 µS, and a sufficient moisturizing effect was not confirmed. . For reference, when the amount of moisture in each layer is measured for the skin in a state in which glycerin has been applied to the skin surface before removal with water 60 minutes after application of glycerin, the increase in electrical conductivity corresponding to the moisturizing effect value, It showed a very high numerical value at 477 µS, and it was confirmed that glycerin is said to be useful as a moisturizing agent. However, considering that glycerin is highly hygroscopic, but this value greatly decreases after glycerin on the skin is removed, the moisturizing effect value before glycerin is removed is measured as the sum of the moisture content in glycerin in addition to the moisture content in each layer. assumed as a result of

[Examples 19 to 23, Comparative Examples 24 to 29]

For emulsions containing the esterified products of Examples 2, 5, 13, 14, and 16, the esterified products of Comparative Example 1, and the oil agents of Comparative Examples 12, 15, 18, and 20, a single test (applied on the skin surface The moisturizing effect in the test in which the number of times was only 1) was investigated.

Specifically, first, emulsions having the formulations shown in Tables 51 and 52 were prepared by the following steps A to C. In addition, as glyceryl stearate, the product "LASEMUL92AE" by Industrial Quimica Lasem (manufactured by IQL), as PEG-100 stearate, the product name "LASEMUL4000" manufactured by IQL, (acrylate/alkyl acrylate (C10) - 30)) As a crosspolymer, the trade name "Pemulen TR-1" manufactured by Lubrizol was used, respectively.

A: Components 1-2 were heated and mixed at 70 degreeC.

B: Components 3 to 10 were uniformly heated and mixed at 70°C.

C: To the mixture obtained in step B, the mixture obtained in step A was added, and emulsified at 2000 rpm at 70°C for 5 minutes with an emulsifier (table-top disper mixer) to obtain an emulsion.

<Evaluation test for moisturizing effect at the time of single application of emulsion>

About the emulsion of Examples 19-23 and Comparative Examples 24-29, 10 panelists performed moisturizing evaluation.

Specifically, the moisturizing effect of the emulsion containing the esterified product was evaluated by applying the emulsion containing the esterified product or the oil to the washed skin and then measuring the moisture content of each layer of the skin after washing with running water.

The moisture content measurement test of each layer of the skin was conducted in the period from autumn to spring when the skin tends to dry. Moreover, in order to eliminate the influence of room temperature and humidity with respect to a measurement result, the test was implemented in the room which adjusted room temperature to 18-22 degreeC and humidity to 40 to 55%.

The moisture content of each layer of the skin was measured as follows.

First, in the same manner as in the above <Test for evaluation of moisturizing effect at the time of single application of an esterified product>, washing of the measurement part, acclimatization to the environment, measurement of blank value, and measurement of the non-coated part were performed.

After that, 40 mg of the emulsion was uniformly applied to the square measurement site of the forearm. Five hours after application, the applied portion was washed with running water (2 L/min) for 20 seconds, excess moisture was wiped off, and the moisture content (µS) of each layer was measured 30 minutes later.

Next, in the same manner as in the above <Test for evaluation of moisturizing effect in single application of esterified product>, the average value of the moisturizing effect values of five panelists obtained using Formulas 1 and 2 was calculated as the moisturizing effect value (µS) of each emulsion. was done with

(Equation 1) [Moisturizing effect value (μS)] = [Moisture content in each layer of the applied part (μS) at the end of the test] - [Moisture amount in each layer of the blank (μS)] - [Amount of moisture in each layer of the uncoated part (μS)] (Equation 2 ) [Amount of moisture in each layer in the uncoated part (μS)] = [Moisture content in each layer in the uncoated part (μS) at the end of the test] - [Moisture content in each layer in the uncoated part (μS) before the start of the test]

Based on the moisturizing effect value (µS) of each emulsion, the moisturizing effect of each emulsion was evaluated according to the criteria in Table 50. The emulsions having a moisturizing evaluation of a4, b4, and c4 were judged to be useful as emulsions having a moisturizing effect, and the emulsions d4 and e4 did not have a moisturizing effect and were judged not to be useful as emulsions having a moisturizing effect. The evaluation results of each emulsion are shown in Tables 51 and 52.

From Tables 51 and 52, even when the emulsion containing the esterified product as the oily moisturizing agent according to the present invention is applied to the skin surface once and then removed from the skin surface, the esterified product of Comparative Example 1 or a commercially available oil It turned out that a higher moisturizing effect was obtained compared with the emulsion of the comparative examples 24-29 which mix|blended. Moreover, it was confirmed that the moisturizing effect value of the emulsion was increased by blending the oil-based moisturizer according to the present invention, even compared to the emulsion without the oil agent (Comparative Example 29).

Industrial Applicability

ADVANTAGE OF THE INVENTION According to this invention, the oil-based moisturizer excellent in the moisturizing effect of skin, and a skin external composition containing the same can be provided.

Claims (7)

It consists of an esterified product of component A and component B or an esterified product of component A, component B and component C, wherein the esterified product has a hydroxyl value of 0 to 160 mgKOH/g;
The mass ratio of the fatty acid residue derived from the component B to the fatty acid residue derived from the component C in the fatty acid residue constituting the ester product of the component A, the component B and the component C is 99.9:0.1 to 45:55, characterized in that Oily moisturizer.
Component A: polyhydric alcohol, which is dipentaerythritol, erythritol, or sorbitan
Component B: one or two or more fatty acids selected from linear saturated fatty acids having 6 to 10 carbon atoms
Component C: 1 type or 2 or more types of fatty acids selected from fatty acids having 6 to 28 carbon atoms (however, component B is excluded) The method of claim 1,
The oily moisturizer wherein the component A is dipentaerythritol. A composition for external use on the skin comprising the oily moisturizer according to claim 1 or 2. 4. The method of claim 3,
The composition for external use on the skin is a cosmetic, a face wash, a systemic cleansing agent, or an external pharmaceutical. A method for moisturizing the skin, wherein the composition for external use on the skin comprising the oily moisturizer according to claim 1 or 2 is applied to the skin surface. An ester product of component A and component B having a hydroxyl value of 0 to 160 mgKOH/g, or
A component A, a component B, and a component having a hydroxyl value of 0 to 160 mgKOH/g and a mass ratio of a fatty acid residue derived from component B to a fatty acid residue derived from component C in the constituent fatty acid residues of 99.9:0.1 to 45:55 Use of C esterified products for moisturizing.
Component A: polyhydric alcohol, which is dipentaerythritol, erythritol, or sorbitan
Component B: one or two or more fatty acids selected from linear saturated fatty acids having 6 to 10 carbon atoms
Component C: 1 type or 2 or more types of fatty acids selected from fatty acids having 6 to 28 carbon atoms (however, component B is excluded) An ester product of component A and component B having a hydroxyl value of 0 to 160 mgKOH/g, or
A component A, a component B, and a component having a hydroxyl value of 0 to 160 mgKOH/g and a mass ratio of a fatty acid residue derived from component B to a fatty acid residue derived from component C in the constituent fatty acid residues of 99.9:0.1 to 45:55 Use of an esterified product of C for producing a composition for external use on the skin.
Component A: polyhydric alcohol, which is dipentaerythritol, erythritol, or sorbitan
Component B: one or two or more fatty acids selected from linear saturated fatty acids having 6 to 10 carbon atoms
Component C: 1 type or 2 or more types of fatty acids selected from fatty acids having 6 to 28 carbon atoms (however, component B is excluded)